JPH09506925A

JPH09506925A - Functional group density control polyamine and method for producing the same

Info

Publication number: JPH09506925A
Application number: JP7517410A
Authority: JP
Inventors: マクグラス，マーテイン・ピーター; トレモント，サミユエル・ジヨージフ
Original assignee: モンサント・カンパニー
Priority date: 1993-12-20
Filing date: 1994-10-27
Publication date: 1997-07-08
Anticipated expiration: 2015-05-08
Also published as: DE69411285T2; SK76096A3; WO1995017440A1; CN1142836A; EP0736048B1; EP0736048A1; ATE167685T1; JP3037758B2; CZ174196A3; AU8127894A; US5559193A; HU9601689D0; BR9408364A; HUT75292A; CA2178649A1; AU679801B2; DE69411285D1

Abstract

(57)【要約】制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基及び反応性炭素−炭素二重結合を含むポリアミンの製造方法であって、制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒド中の本質的に全アルデヒド基を第１の第２アミン基で還元的アミノ化し、ポリ（第３アミン）を生成する段階と、制御された量のペンダントアルデヒド基をもつポリ（第３アミン）をヒドロホルミル化する段階と、ペンダントアルデヒド基をもつポリ（第３アミン）を第１アミン又は第２の第２アミンで還元的アミノ化する段階を含む方法。ポリアミンを製造する本発明の別の態様では、所定量の第１の第２アミンでポリアルデヒドを還元的アミノ化して制御された量のアルデヒド基を還元的アミノ化し、更に第１アミン又は第２の第２アミンで還元的アミノ化して残りの実質的に全アルデヒド基を還元的アミノ化する。制御された量のペンダント第３及び第２アミン基を含むポリアミンを製造する本発明の更に別の態様では、所望の制御された量のペンダント第３アミン及び第２アミン基をもつポリアミンを生成するために必要な相対量の第２アミンと第１アミンの混合物でポリアルデヒドを還元的アミノ化する。 (57) [Summary] A process for the preparation of a polyamine comprising a controlled amount of a pendant tertiary amine group and a controlled amount of a pendant secondary amine or a different tertiary amine group and a reactive carbon-carbon double bond, the controlled amount of A reductive amination of essentially all aldehyde groups in a polyaldehyde containing pendant aldehyde groups and reactive carbon-carbon double bonds with primary secondary amine groups to form poly (tertiary amines). Hydroformylating a poly (tertiary amine) with a controlled amount of pendant aldehyde groups, and reducing the poly (tertiary amine) with pendant aldehyde groups with a primary amine or a secondary secondary amine. A method including the step of embodying. In another aspect of the invention for making a polyamine, a reductive amination of a polyaldehyde with a predetermined amount of a first secondary amine to reductively aminate a controlled amount of an aldehyde group further comprises a primary amine or a secondary amine. To reductively aminate the remaining substantially all aldehyde groups. Yet another aspect of the present invention for making polyamines containing controlled amounts of pendant tertiary and secondary amine groups produces a desired controlled amount of polyamines having pendant tertiary and secondary amine groups. The polyaldehyde is reductively aminated with a mixture of the secondary and primary amines in the required relative amounts.

Description

【発明の詳細な説明】官能基密度制御ポリアミンとその製造方法発明の背景本発明はオレフィン性不飽和を含む官能基密度制御ポリアミン（ｃｏｎｔｒｏｌｌｅｄｆｕｎｃｔｉｏｎａｌｄｅｎｓｉｔｙｐｏｌｙａｍｉｎｅｓ）に関する。１側面において、本発明は制御された量のペンダント（ｐｅｎｄａｎｔ）第３アミン及びペンダント第２アミン基をもつ官能基密度制御ポリアミンの製造に関する。別の側面において、本発明は制御された量の２種の異なるペンダント第３アミン基をもつ官能基密度制御ポリアミンの製造に関する。更に別の側面において、本発明はオレフィン性不飽和を含む出発ポリマー中の炭素−炭素二重結合の選択的反応によるオレフィン性不飽和を含む官能基密度制御ポリアミンの製造に関する。オレフィンを水素、一酸化炭素及び第１又は第２アミンと反応させてアミンを製造する原理は知られている。種々の触媒を使用してこの原理を具体化する種々の方法が報告されている。このような方法は一般にアミノメチル化反応と呼ばれる。Ｊ．Ｏｒｇ．Ｃｈｅｍ．，４７，４４５（１９８２）においてＪａｃｈｉｍｏｗｉｃｚらはオレフィンからアミンへの有効且つ一般的な１段階変換を考案する試みで使用した種々のアプローチを開示している。触媒としてペンタカルボニル鉄、酸化ロジウム、ルテニウム／鉄カルボニル及びイリジウム触媒が挙げられている。米国特許第４，２９７，４８１号は、少なくとも２個のレービル（ｌａｂｉｌｅ）水素が窒素原子に結合したモノマー窒素化合物、少なくとも２個のオレフィン基を含むモノマー炭化水素化合物、一酸化炭素及び水を触媒量のロジウム含有化合物の存在下で接触させることにより、アミノ／アミド窒素をポリマー主鎖（ｂａｃｋｂｏｎｅ）に含む高分子ポリアミン／アミドを形成する方法を開示している。この発明はアンモニア又は第１アミンの使用を記載しているが、ペンダント第２アミン基のみをもつポリマーは製造していないし、ペンダント第２及び第３アミン基の量を制御可能なポリマーも製造していない。ペンダントアミン及びアミド基をもつポリマーの製造は米国特許第４，３１２，９６５号に記載されている。これらのポリマーは高分子ポリオレフィン、一酸化炭素、水、及びアンモニアや第１又は第２アミンなどの窒素化合物から製造される。ここでもロジウム又はロジウム含有化合物が触媒として用いられている。しかし、この発明に記載されたポリマーはアミン取込度が低く、第１アミンを出発材料として使用する場合には第３アミン基が大半を占め、ペンダント第２及び第３アミン基の量を制御することができない。米国特許第４，５０３，２１７号はルテニウム含有触媒を含む触媒系と、生成物ポリアミンを容易に分離できるように２相液体生成物を提供するジメチルホルムアミド−アルカン混合溶剤の存在下でポリブタジエン、アンモニア及び第１又は第２アミン、一酸化炭素並びに水素から高分子ポリアミンを製造する方法を教示している。この発明で第１アミンを使用する場合には、ビニル基しか官能化されず、アミン含有ポリマーの収率は低く、得られるポリマーは有機溶剤に不溶性である。米国特許第４，６５７，９８４号は触媒としてルテニウム又はロジウムホスフィンを使用して一酸化炭素、水素、高分子オレフィン及び第２アミンから高分子ポリ（第３アミン）を製造する方法を開示している。この特許は、これらの特定触媒を使用すると反応が助長され、ひいては内部及びビニルオレフィン基の官能化が助長されると述べている。このように、高分子第２及び第３ポリアミンの製造に関する従来技術は、種々の条件下で種々の触媒を使用してビニルオレフィンと内部オレフィンを反応させ得るアミノメチル化反応を教示している。しかしながら、アミノメチル化従来技術はポリアルデヒド又はポリアルデヒドから製造されるポリアミンの官能化度即ち官能基密度、特に種々のアミンペンダント基の量の制御方法について何ら教示していないので、これらの反応はヒドロホルミル化及び還元的アミノ化の反応シーケンスとは著しく異なる。より温和な反応条件を使用して、その結果、制御された量のペンダント第３アミン及びペンダント第２アミン基、又は制御された量の２種の異なるペンダント第３アミン基を含む官能基密度の高いポリマーを生じ、有機溶剤に可溶性のポリマーを生成する、残留反応性炭素−炭素二重結合を含む官能基密度制御ポリアミンの製造方法が実現されるならば極めて望ましいことである。本発明の方法により製造されるポリアミンはゴム薬品で有用であり、例えば硬化中に危険な揮発性物質を放出しないポリマー結合硬化促進剤、ある成分から別の成分に移動できない高分子補助活性剤（ｃｏ−ａｃｔｉｖａｔｏｒｓ）、及びゴム製品（例えばタイヤ）から浸出する傾向が著しく低いポリマー結合酸化防止剤及び／又はオゾン亀裂防止剤などに用いられる。本発明の方法により製造される制御された量のペンダント第３アミン基及びペンダント第２アミン基をもつポリアミンは、ウレタン／尿素材料、コーティング、接着剤、シーラントにも有用であり、該ポリアミンがペンダント第２アミン基を含む場合には第３アミンに利用できない結合を介する三次元的網状構造の構築にも有用である。発明の概要本発明の１目的は、オレフィン性不飽和を含む官能基密度制御ポリアミンの製造方法を提供することである。本発明の別の目的は、制御された量のペンダント第３及び第２アミン基又は制御された量の２種の異なる第３アミン基を含み且つペンダント第２アミン基から誘導される第３アミン基を実質的に含まず、有機溶剤に可溶性の官能基密度の高いポリマーを生成する、効率的で商業的に実施可能な、温和な反応条件を使用して行う残留反応性炭素−炭素二重結合を含む官能基密度制御ポリアミンの製造方法を提供することである。本発明の更に別の目的は、硬化促進剤、高分子補助活性剤及び酸化防止剤／オゾン亀裂防止剤などのゴム薬品用途で使用するための官能基密度制御ポリアミンの製造方法を提供することである。本発明によると、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法が提供され、該方法は、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物（ａｌｋａｌｉｍｅｔａｌｂｏｒｏｈｙｄｒｉｄｅ）の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを第１の第２アミンと接触させて、第３アミン基と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリ（第３アミン）を生成する段階と、ヒドロホルミル化触媒の存在下にヒドロホルミル化条件下で反応性炭素−炭素二重結合を含むポリ（第３アミン）を一酸化炭素及び水素と接触させて、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を第１アミン又は第２の第２アミンと反応させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリアミンを生成する段階とを含み、但し制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ(第３アミン)の還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。１態様において、還元的アミノ化は一酸化炭素の存在下で実施される。別の態様において、ポリアルデヒドは、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。更に別の態様において、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒド又はポリ（第３アミン）中のアルデヒド基の量は、ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される。更に本発明によると、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法が提供され、該方法は、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを、還元的アミノ化すべきペンダントアルデヒド基の百分率に依存する量の第１の第２アミンと接触させて、ポリ（第３アミン）中のペンダント第３アミン基及びペンダントアルデヒド基の和と反応性炭素−炭素二重結合の比がポリアルデド中のペンダントアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しくなるように、制御された量のペンダント第３アミン基、制御された量のペンダントアルデヒド基及び制御された量の反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下でポリ（第３アミン）を第１アミン又は第２の第２アミンと接触させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比がポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリアミンを生成する段階とを含み、但し還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。１態様において、還元的アミノ化は一酸化炭素の存在下で実施される。別の態様において、ポリアルデヒドは、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。更に別の態様において、ポリアルデヒドの官能基密度、即ちオレフィン性不飽和を含むポリマー中でアルデヒド基にヒドロホルミル化される炭素−炭素二重結合のモル百分率は、ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される。更に本発明によると、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン基を含むポリアミンの製造方法が提供され、該方法は、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び炭素−炭素二重結合を含むポリアルデヒド、第１の第２アミン及び第１アミンを接触させて、第３アミン基及び第２アミン基数の和と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリ（第２／第３アミン）を生成する段階を含み、第１の第２アミンと第１アミンのモル比は第１の第２アミンと第１アミンの相対反応性及びペンダント第３アミン及びペンダント第２アミン基の所望の制御された量に依存し、但し還元的アミノ化がアルカリ金属ホウ水素化物の存在下で実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。１態様において、還元的アミノ化は一酸化炭素の存在下で実施される。別の態様において、ポリアルデヒドは、ヒドロホルミル化触媒の存在下でオレフィン性不飽和を含むポリマーを一酸化炭素及び水素と接触させることにより生成される。更に別の態様において、ポリアルデヒド中のアルデヒド基の量は、ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される。更に本発明によると、反応性炭素−炭素二重結合をもつオレフィン性不飽和を含むポリマーの反復単位から誘導される反復単位と、オレフィン性不飽和を含む同一ポリマーで且つヒドロホルミル化され、ペンダント第２アミン及び第３アミン基を生成するように還元的アミノ化されたポリマーの反復単位から誘導される反復単位とを含むポリアミンが提供され、ポリアミンの官能基密度は２〜約９０モル％であり、ペンダント第３アミン基をもつ反復単位数は、ペンダント第３及び第２アミン基をもつ反復単位数の和の約５〜約９５％であり、但しペンダント第２アミン基をもつ反復単位及びペンダント第３アミン基をもつ反復単位の数は、反応性炭素−炭素二重結合を含む反復単位とペンダント第２及び第３アミン基を含む反復単位の数の和の各々少なくとも１％である。更に本発明によると、反応性炭素−炭素二重結合をもつオレフィン性不飽和を含むポリマーの反復単位から誘導される反復単位と、オレフィン性不飽和を含む同一ポリマーであり且つヒドロホルミル化され、２種の異なる第３アミン基をもつ反復単位を生成するように還元的アミノ化されたポリマーの反復単位から誘導される反復単位とを含むポリアミンが提供され、ポリアミンの官能基密度は２〜約９０モル％であり、第２アミンの一方から誘導されるペンダント第３アミン基をもつ反復単位の数は、ペンダント第３アミン基をもつ反復単位の数の合計の約５〜約９５％であり、但し第１の第２アミンから誘導されるペンダント第３アミン基をもつ反復単位の数及び第２の第２アミンから誘導されるペンダント第３アミン基をもつ反復単位の数は、反応性炭素−炭素二重結合をもつオレフィン性不飽和を含む反復単位とペンダント第３アミン基をもつ反復単位の数の和の各々少なくとも１％である。発明の詳細な説明本発明の第１の態様は、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法に関し、該方法は、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを第１の第２アミンと接触させて、第３アミン基と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリ（第３アミン）を生成する段階と、（ｂ）ヒドロホルミル化触媒の存在下にヒドロホルミル化条件下で反応性炭素−炭素二重結合を含むポリ（第３アミン）を一酸化炭素及び水素と接触させて、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（ｃ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を第１アミン又は第２の第２アミンと反応させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリアミンを生成する段階とを含み、但し(ｃ)の還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。本発明の第１の態様の方法によると、（ａ）のポリアルデヒドはオレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。また、還元的アミノ化が水素とルテニウム含有イミン水素化触媒の存在下で実施される場合には、（ａ）又は（ｃ）の還元的アミノ化は場合により一酸化炭素の存在下で実施され得る。還元的アミノ化中に一酸化炭素が存在する場合、一酸化炭素と水素のモル比は約０．１５：１未満、好ましくは約０．１：１未満、最適には約０．０５：１未満である。本発明の第２の態様は制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法に関し、該方法は、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを、還元的アミノ化すべきペンダントアルデヒド基の百分率に依存する量の第１の第２アミンと接触させて、ポリ（第３アミン）中のペンダント第３アミン基及びペンダントアルデヒド基の和と反応性炭素−炭素二重結合の比がポリアルデド中のペンダントアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しくなるように、制御された量のペンダント第３アミン基、制御された量のペンダントアルデヒド基及び制御された量の反応性炭素− 炭素二重結合を含むポリ（第３アミン）を生成する段階と、（ｂ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で（ａ）のポリ（第３アミン）を第１アミン又は第２の第２アミンと接触させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が（ａ）のポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリアミンを生成する段階とを含み、但し（ｂ）の還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。本発明の第２の態様の方法によると、ポリアルデヒドは、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。また、（ａ）又は（ｂ）の還元的アミノ化が水素とルテニウム含有イミン水素化触媒の存在下で実施される場合には、還元的アミノ化は場合により一酸化炭素の存在下で実施され得る。還元的アミノ化中に一酸化炭素が存在する場合、一酸化炭素と水素のモル比は約０．１５：１未満、好ましくは約０．１：１未満、最適には約０．０５：１未満である。本発明の第３の態様は制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン基を含むポリアミンの製造方法に関し、該方法は、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基と炭素−炭素二重結合を含むポリアルデヒド、第１の第２アミン及び第１アミンを接触させて、第３アミン基及び第２アミン基数の和と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しいポリ（第２／第３アミン）を生成する段階を含み、第１の第２アミンと第１アミンのモル比は第１の第２アミンと第１アミンの相対反応性及びペンダント第３アミン及びペンダント第２アミン基の所望の制御された量に依存し、但し還元的アミノ化がアルカリ金属ホウ水素化物の存在下で実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。本発明の第３の態様の方法によると、ポリアルデヒドはオレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。また、還元的アミノ化が水素とルテニウム含有イミン水素化触媒の存在下で実施される場合には、還元的アミノ化は場合により一酸化炭素の存在下で実施され得る。還元的アミノ化中に一酸化炭素が存在する場合、一酸化炭素と水素のモル比は約０．１５：１未満、好ましくは約０．１：１未満、最適には約０．０５：１未満である。本発明により製造されたポリアミンは容易に回収でき、ゴム薬品、ウレタン／尿素材料、コーティング、接着剤、シーラントに好適であり、ポリアミンがペンダント第２アミン基を含む場合には第３アミンに利用できない結合を介する三次元網状構造の構築にも好適である。本発明の第４の態様は、式：（式中、Ｐ₁を含む反復単位及びＰ₂を含む反復単位は、ヒドロホルミル化及び還元的アミノ化されたオレフィン性不飽和を含むポリマーの反復単位を表し、Ｐ₃ は反応性炭素−炭素二重結合をもつオレフィン性不飽和を含む同一ポリマーの反復単位を表し、Ｒ、Ｒ’及びＲ”は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択され、Ｐ₁ を含む反復単位とＰ₂を含む反復単位の和は、Ｐ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の和の約２〜約９０％であり、Ｐ₂を含む反復単位の数はＰ₁ を含む反復単位とＰ₂を含む反復単位の数の和の約５〜約９５％であり、但しＰ₁を含む反復単位とＰ₂を含む反復単位の数はＰ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の数の和の各々少なくとも１％である）の反復単位を含むポリアミンに関する。置換脂肪族、芳香族及び脂環式基の置換基は、（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅及びＲ₆は独立して水素、脂肪族基、芳香族基及び脂環式基から構成される群から選択され、但しＲ₁及びＲ₂の少なくとも一方とＲ₅ 及びＲ₆の少なくとも一方は水素以外のものであり、Ｒ₄は脂肪族基、芳香族基及び脂環式基から構成される群から選択され、ｍは０〜４の整数であり、ｎは１〜７の整数である）及びその混合物から構成される群から選択される。本発明により製造されるポリアミンは式：の反復単位を本質的に含まず、換言するならばペンダントアルデヒド基を含むポリアルデヒド又はポリ（第３アミン）中のアルデヒド基の本質的に全部が還元的アミノ化中にアミン基に変換される。更に、本発明により製造されるポリアミンが式：のペンダント第２アミン基を含むとき、ポリアミンは式：（式中、Ｒ’は脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基及びその組み合わせから構成される群から選択される）の反復単位を本質的に含まず、換言するならばポリアミンはペンダント第２アミン基から誘導される第３アミン基を本質的に含まない。本発明の第５の態様は式：（式中、Ｐ₁を含む反復単位及びＰ₂を含む反復単位は、ヒドロホルミル化及び還元的アミノ化されたオレフィン性不飽和を含むポリマーの反復単位を表し、Ｐ₃ は反応性炭素−炭素二重結合をもつオレフィン性不飽和を含む同一ポリマーの反復単位を表し、Ｒ、Ｒ’、Ｒ”及びＲ’”は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択され、但し−ＮＲＲ’は−ＮＲ”Ｒ’”と異なり、Ｐ₁を含む反復単位とＰ₂を含む反復単位の和は、Ｐ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の和の２〜約９０％であり、Ｐ₁を含む反復単位の数はＰ₁を含む反復単位とＰ₂を含む反復単位の数の和の約５〜約９５％であり、但しＰ₁を含む反復単位とＰ₂を含む反復単位の数はＰ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の数の和の各々少なくとも１％である）の反復単位を含むポリアミンに関する。置換脂肪族、芳香族及び脂環式基の置換基は上記に定義した通りである。ヒドロホルミル化本発明によると、ポリアミンは本発明により製造したオレフィン性不飽和を含むポリマー又は反応性炭素−炭素二重結合を含むポリ（第３アミン）をヒドロホルミル化することにより得られるアルデヒド官能化ポリマーから製造される。本発明の方法で有用なオレフィン性不飽和を含むポリマーは、複数の炭素−炭素二重結合をもつＣ₄−Ｃ₁₀モノマー（例えばブタジエン、イソプレン、シクロペンタジエン）、シクロペンタジエン、１，３−ペンタジエン、１，４−ペンタジエン、１，３−ヘキサジエン、１，４−ヘキサジエン、１，５−ヘキサジエン、２，４−ヘキサジエン、１，３，５−ヘキサトリエン等のダイマーから形成されるホモポリマーであり得る。本発明で使用されるオレフィン性不飽和を含むポリマーは、その異性立体配置の任意のものであり得る。例えばポリブタジエンの場合には、シス−１，４、トランス−１，４もしくはトランス−１，２配置又はその混合物であり得る。更に、本発明の方法で有用なポリマーは炭素−炭素二重結合を含むポリマーセグメントを形成することが各々可能な２種以上のモノマー化合物から形成されるコポリマーでもよく、例えばポリブタジエンセグメントをもつコポリマー、具体的には例えばポリ（ブタジエン−イソプレン）、ポリ（ブタジエン−１，４−ペンタジエン）等のコポリマーである。本発明の方法で有用なオレフィン性不飽和を含むポリマーは、オレフィンを含むポリマーセグメントを生成することが可能な上記のような少なくとも１種のモノマーと、オレフィンを含むポリマーセグメントを形成しない少なくとも１種の共重合性ビニルモノマー［例えばアクリルアミド、アクリロニトリル、スチレン、アクリレート、アルキルビニルエーテル、アルキルビニルケトン等及びその混合物並びにこのようなモノマーのＣ₁ −Ｃ₂₀ヒドロカルビル誘導体（例えばα−メチルスチレン、メチルアクリレート等）］から形成されるコポリマーでもよい。このような材料は周知の通り、ラジカル、カチオン又はアニオン重合法により慣用方法で形成される。これらのポリマーは、ポリ（ブタジエン−アクリロニトリル）、ポリ（ブタジエン−スチレン）、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂、エチレン−プロピレン−ジエン（ＥＰＤＭ）ポリマーなど多種多様のものを市販品として容易に入手できる。オレフィン性不飽和を含むポリマーは、生成されるポリマーが所望のポリアルデヒド生成物の活性前駆物質として機能するために十分な量の炭素 −炭素二重結合を含む限り、任意の所望の程度までオレフィンを含まないモノマー基を用いて形成することができる。本発明の方法で有用なオレフィン性不飽和を含むポリマーは、枝分かれ、異性化等により残留炭素−炭素二重結合を含むポリマー材料を生成するオレフィン性モノマー（例えばエチレン、プロピレン、１−ブテン、１ −ペンテン、１−ヘキセン、２−メチル−１−プロペン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、３，３−ジメチル−１−ブテン、２，４，４ −トリメチル−１−ペンテン、３−メチル−１−ヘキセン、３−メチル−１−ブテン等）から形成することもできる。オレフィン性不飽和を含む適切なポリマーとしては、ポリエチレン、ポリプロピレン、ポリブテン、ポリブタジエン及びポリオクテン等のホモポリマー；ポリ（エチレンプロピレン）、ポリ（エチレンオクテン）、ポリ（エチレンイソブチレン）、ポリ（エチレン−１−ブテン）、ポリ（エチレンヘキセン）及びポリ（プロピレンオクテン）等のオレフィンのコポリマー；オレフィンと少なくとも１種の共重合性モノオレフィンモノマーのコポリマー、例えば２種以上のオレフィンとジエンモノマーのコポリマー、具体的にはポリ（エチレンプロピレンジエンモノマー）（ＥＰＤＭ）、ポリ（エチレンビニルアセテート）、ポリ（エチレンビニルアルコール）、ポリ（エチレンエチルアクリレート）、ポリ（プロピレンメチルアクリレート）、ジエンとアクリロニトリルのコポリマー（例えばブタジエンとアクリロニトリルのコポリマー）等が挙げられる。満足なジエンモノマーとしては、１，４−ヘキサジエン、２−メチル−２，４ −ペンタジエン、１，４，９−デカトリエン及び１１−エチル−１，１１−トリデカジエン等の直鎖（非環式）ジエン；１，５−シクロオクタジエン等の単環式ジエン；５−エチリデンノルボルネン（ＥＮＢ）、５−メチレン−２−ノルボルネン、５−イソプロピリデン−２−ノルボルネン及び２−メチル−ビシクロ−（２．２．１）−２，５−ヘプタジエン等のジエン；ビシクロ−（４．３．０）− ３，７−ノナジエン、５−メチル−ビシクロ−（４．３．０）−３，７−ノナジエン、５，６−ジメチル−ビシクロ−（４．３．０）−３，７−ノナジエン及びビシクロ−（３．２．０）−２，６−ヘプタジエン等の縮合環二環式ジエン；４ −ビニルシクロヘキセン、１，２−ジビニルシクロブタン及び１，２，４−トリビニルシクロヘキサン等のアルケニル置換単環式ジエン；及びジシクロペンタジエン（ＤＣＰＤ）等の三環式ジエンが挙げられる。本発明の実施で使用するのに適したＥＰＤＭゴムのグレードは市販されている。ＲｕｂｂｅｒＷｏｒｌｄＢｌｕｅＢｏｏｋ１９７５Ｅｄ．，ＭａｔｅｒｉａｌｓａｎｄＣｏｍｐｏｕｎｄｉｎｇＩｎｇｒｅｄｉｅｎｔｓｆｏｒＲｕｂｂｅｒ，ｐｐ４０６−４１０。好適ＥＰＤＭゴムはＵｎｉｒｏｙａｌＣｈｅｍｉｃａｌＣｏｍｐａｎｙ，Ｉｎｃ．，Ｍｉｄｄｌｅｂｕｒｙ，ＣＴから商品名Ｔｒｉｌｅｎｅ（登録商標）で市販されており、例えばＴｒｉｌｅｎｅ（登録商標）６６及び６７（ＥＮＢジエンモノマー）、Ｔｒｉｌｅｎｅ（登録商標）５５及び６５（ＤＣＰＤジエンモノマー）などがある。他の好適ＥＰＤＭゴムとしては、ジエンモノマーが５−イソプロピリデン −２−ノルボルネンであるものが挙げられる。特に必要ではないが、このようなＥＰＤＭゴムにおけるエチレンとプロピレンの比は約４０／６０〜約５０／５０の範囲が好ましい。本発明で有用なオレフィン性不飽和を含む好適ポリマーはポリブタジエンとポリ（エチレンプロピレンジエンモノマー）である。ヒドロホルミル化反応を受けるために、オレフィン性不飽和を含むポリマー又は反応性炭素−炭素二重結合を含むポリ（第３アミン）はある程度の不飽和を含まなければならず、即ち合成ガス（一酸化炭素と水素）がアルデヒド（−ＣＨＯ）基を形成する部位である炭素−炭素二重結合を含まなければならない。この不飽和はポリマーの主鎖及び／又はそのペンダント（例えばＥＰＤＭポリマーの場合）に存在し得る。好ましくは、オレフィン性不飽和を含むポリマー中の不飽和度は１ポリマー鎖（又は分子）当たり１個の炭素−炭素二重結合から４炭素原子当たり約１個の炭素−炭素二重結合までの範囲である。ポリマーの不飽和度の測定方法は周知である。例えば、不飽和度はＡＳＴＭＤ−１６３８−５９Ｔにより測定することができる。赤外分光法又は¹ＨＮＭＲを用いて不飽和度を測定することもできる。この方法はＷｉｌｌａｒｄら，ＩｎｓｔｒｕｍｅｎｔａｌＭｅｔｈｏｄｓｏｆＡｎａｌｙｓｉｓ，第５及び６章，ＶａｎＮｏｓｔｒａｎｄＣｏ．，Ｉｎｃ．，Ｐｕｂｌｉｓｈｅｒｓ（１９６５）に記載されているような周知方法により実施することができる。あるいは、周知滴定方法も使用できる。不飽和度の好適測定方法は¹ ＨＮＭＲである。オレフィン性不飽和を含む適切なポリマーは約３００〜約２５０，０００、好ましくは約６００〜約１５０，０００、最適には約１０００〜約１５，０００の重量平均分子量（Ｍ_w）をもつポリマーである。オレフィン性不飽和を含むポリマー又は反応性炭素−炭素二重結合を含むポリ（第３アミン）を溶融相として又は不活性溶剤に溶解して一酸化炭素及び水素と混合する。溶剤を使用しない場合には、特定ポリマーに対応するガラス転移温度（Ｔ_g）よりも高温までポリマーを加熱した後、一酸化炭素と水素を加えて混合する。不活性溶剤を使用する場合には、ポリマーを溶剤に溶かした後、一酸化炭素と水素を加えて混合する。ポリマーを溶かすのに適した不活性溶剤としてはトルエン及びトルエン／ジメチルホルムアミド混合物が挙げられる。水素及び一酸化炭素は、水素と一酸化炭素のモル比が約１：３〜約３：１、好ましくは約１：２〜約２：１、最適には約１：１となるようにポリマーと混合する。反応の全工程中、水素と一酸化炭素を本質的に初期モル比に維持するのが好ましい。一酸化炭素と水素の添加後、適切な触媒を混合物に加える。あるいは、水素と一酸化炭素を加える前に触媒をポリマーと接触させてもよい。オレフィン性不飽和を含むポリマーをヒドロホルミル化するのに適切な触媒の非限定的な例はVIII族金属触媒である。好適VIII族金属はロジウム（Ｉ）である。適切なロジウム（Ｉ）触媒の例としては、ジカルボニルアセチルアセトナートロジウム（Ｉ）（Ｒｈ（ＣＯ）₂ＡｃＡｃ）、シクロオクタジエントリフルオロアセチルロジウム（Ｉ）ダイマー（［Ｒｈ（ＣＯＤ）（Ｏ₂ＣＣＦ₃）］₂）、ＲｈＨ（ＣＯ）（ＰＰｈ₃）₃等が挙げられる。好適ヒドロホルミル化触媒はＲｈ（ＣＯ）₂ＡｃＡｃとＲｈＨ（ＣＯ）（ＰＰｈ₃）₃である。ヒドロホルミル化反応は一酸化炭素／水素雰囲気下で実施される。ヒドロホルミル化反応中の一酸化炭素／水素の圧力は約５０ｐｓｉｇ〜約１０００ｐｓｉｇ、好ましくは約２００ｐｓｉｇ〜約１０００ｐｓｉｇである。ヒドロホルミル化反応の温度は約２５℃〜約２００℃、好ましくは約５０℃〜約１５０℃、最適には約８０℃〜約１２０℃である。ヒドロホルミル化反応中に生成されるペンダントアルデヒド基を含むポリアルデヒド又はポリ（第３アミン）の官能基密度は、オレフィン性不飽和を含む出発ポリマー又は反応性炭素−炭素二重結合を含むポリ（第３アミン）中に存在する不飽和度に関連する一酸化炭素と水素の量により異なる。ポリアルデヒドの官能基密度は、ヒドロホルミル化反応中の一酸化炭素／水素ガス取込を測定することにより制御される。こうしてオレフィン性不飽和を含むポリマー又は反応性炭素−炭素二重結合を含むポリ（第３アミン）上に位置するアルデヒドの量を測定及び制御することができる。所望の官能基密度に達したら反応を停止できる。ヒドロホルミル化触媒、特にロジウム（Ｉ）触媒は金属ロジウムで換算してオレフィン性不飽和を含むポリマー１０⁶部当たり約２００部未満の割合でヒドロホルミル化反応に使用される。従って、ヒドロホルミル化反応は経済的に実施することができ、即ち触媒費用が安価で比較的温和な条件で実施できる。本発明の方法は、オレフィン性不飽和を含むポリマー中でアルデヒド基にヒドロホルミル化される炭素−炭素二重結合のモル％として官能基密度を表した場合にポリアルデヒドの官能基密度を２モル％から約９０モル％までの範囲で制御することができる。本発明の方法はポリアルデヒドの官能基密度を上記範囲内で任意の値に制御できるが、約１０モル％〜約８５モル％の範囲の官能基密度とするのが好ましい。同様に、反応性炭素−炭素二重結合を含むポリ（第３アミン）をヒドロホルミル化する場合には、本発明の方法はポリ（第３アミン）の合計官能基密度が２モル％〜約９０モル％となるように、ポリ（第３アミン）中の利用可能な反応性炭素−炭素二重結合をヒドロホルミル化することにより生成されるアルデヒド基の官能基密度を制御することができる。合計官能基密度は、オレフィン性不飽和を含むポリマー中で第３アミン基への還元的アミノ化前後にアルデヒド基にヒドロホルミル化される炭素−炭素二重結合のモル％である。１態様では還元的アミノ化前にポリアルデヒドを回収することができる。ポリアルデヒドを回収する場合には、任意の慣用回収方法で回収することができる。例えば溶剤（例えばトルエン）の存在下でヒドロホルミル化反応を行う場合には、反応混合物中の溶剤量を減らし、混合物を撹拌しながらメタノールをゆっくりと加えてポリアルデヒドを沈殿させる。次いでポリマーを回収し、元の溶剤に再溶解し、メタノールで再び沈殿させる。こうして精製ポリアルデヒドを回収することができる。還元的アミノ化還元的アミノ化は、ルテニウム含有イミン水素化触媒の存在下に適切な溶剤中で上記ポリアルデヒドを第１の第２アミン及び水素と反応させるか、又はアルカリ金属ホウ水素化物の存在下で上記ポリアルデヒドを第１の第２アミンと反応させることにより実施される。本発明の方法により製造されるポリ（第３アミン）は、第３アミン基と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しい。制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）の還元的アミノ化は、ルテニウム含有イミン水素化触媒の存在下に適切な溶剤中でポリ（第３アミン）を第１アミン又は第２の第２アミン及び水素と反応させるか、又はアルカリ金属ホウ水素化物の存在下で上記ポリ（第３アミン）を第１アミン又は第２の第２アミンと反応させることにより実施され、但し還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。本発明の方法により製造されるポリアミンは、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に実質的に等しい。ポリアミン及び／又はポリ（第３アミン）の官能基密度は、ポリアルデヒド及び／又はポリ（第３アミン）中のアルデヒド基の官能基密度に依存する。従って、ポリアミンの官能基密度は、合計ペンダントアミン官能基密度が出発ポリアルデヒドを製造するために使用するオレフィン性不飽和を含むポリマー中の炭素− 炭素二重結合のレベルに基づき２モル％〜約９０モル％の範囲となるように容易に制御することができる。従って、ポリアミン中の合計ペンダントアミン官能基密度はポリアミンの最終用途に所望される特定官能基密度に依存して２モル％〜約９０モル％、好ましくは約１０モル％〜約８５モル％の範囲の任意の値であり得る。ポリアミン中の第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度は合計ペンダントアミン官能基の約５〜約９５％であり、但し第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％であり、ペンダント第２アミン基又は第２の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％である。従って、合計ペンダントアミン官能基の残余はポリアミン中のペンダント第２アミン基又は第２の第２アミンから誘導されるペンダント第３アミン基の官能基密度から誘導される。ルテニウム含有イミン水素化触媒を使用する本発明の方法で使用するのに適切なアミンは式ＲＲ’ＮＨ（式中、Ｒ及びＲ’は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択される）により表される第２アミン、及び式ＲＮＨ₂（式中、Ｒは上記と同義である）により表される第１アミンである。第１の第２アミンと第２の第２アミンを使用する本発明の態様では、Ｒ及びＲ’は第１の第２アミンが第２の第２アミンと異なるように選択される。置換脂肪族、置換芳香族及び置換脂環式基の場合には、脂肪族、脂環式又は芳香族基上の置換基は、（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅及びＲ₆は独立して水素、脂肪族基、芳香族基及び脂環式基から構成される群から選択され、但しＲ₁及びＲ₂の少なくとも一方とＲ₅ 及びＲ₆の少なくとも一方は水素以外のものであり、Ｒ₄は脂肪族基、芳香族基及び脂環式基から構成される群から選択され、ｍは０〜４の整数であり、ｎは１〜７の整数である）及びその混合物から構成される群から選択される。本発明の方法で置換第１又は第２アミンを使用する場合には、好適置換基は−ＯＲ₁及び −ＮＲ₁Ｒ₂から構成される群から選択され、最適置換基は、Ｒ₁及びＲ₂の一方が水素であり且つＲ₁及びＲ₂の他方が脂肪族又は脂環式基である−ＮＲ₁Ｒ₂である。本明細書中で使用する「芳香族」なる用語は、１個以上の環を含み、好ましくは６〜約１４個の炭素原子を含む不飽和環式炭化水素を意味する。芳香族環の非限定的な例としてはフェニル、ナフチル等が挙げられる。本明細書中で使用する「脂肪族」なる用語は炭素原子数１〜約２２の直鎖又は枝分かれ鎖炭化水素を意味する。本明細書中で使用する「脂環式」なる用語は脂環式化合物、即ち閉環構造中に炭素原子配置を含み、炭素原子数３〜約１８、好ましくは３〜約８の炭化水素化合物を意味する。脂環式環の非限定的な例としてはシクロプロピル、シクロペンチル、シクロヘキシル、シクロオクチル等が挙げられる。適切な第１アミンの非限定的な例としては、メチルアミン、エチルアミン、イソプロピルアミン、ｎ−ブチルアミン、ｎ−ヘキシルアミン、ｎ−オクチルアミン、２−アミノヘプタン、シクロヘキシルアミン、シクロオクチルアミン、アニリン、ベンジルアミン、２−アミノエタノール、４−アミノ−１−ブタノール、２−アミノ−１−ブタノ−ル、６−アミノ−１−ヘキサノール、２−アミノ−１ −メトキシプロパン、４−アミノフェノール、４−アミノシクロヘキサノール、４−アミノベンゾトリフルオリド、Ｎ−イソプロピル−４−アミノフェニルアミン、Ｎ−（２−ブチル）−４−アミノフェニルアミン、Ｎ−メチルイソアミル− ４−アミノフェニルアミン、Ｎ−シクロヘキシル−４−アミノフェニルアミン、Ｎ−オクチル−４−アミノフェニルアミン、４−アミノジフェニルアミン、Ｎ，Ｎ−ジメチルエチレンジアミン等が挙げられる。適切な第２アミンの非限定的な例としてはジメチルアミン、ジエチルアミン、メチルエチルアミン、ｎ−メチルエタノールアミン、ジ（ｎ−プロピル）アミン、ジ（エチルヘキシル）アミン、ピペリジン、モルホリン、ピペラジン、ジ（ｎ−ヘプチル）アミン、Ｎ−メチルアニリン、２−アミノオクタン、４−アミノジフェニルアミン、Ｎ−フェニル−Ｎ ’−シクロヘキシル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ビス−（１−メチルプロピル）−ｐ−フェニレンジアミン、ジベンジルアミン、メチルナフチルアミン等が挙げられる。アルカリ金属ホウ水素化物を使用する本発明の方法で使用するのに適切なアミンは上記のような第２アミン、立体障害脂肪族又は脂環式第１アミン、芳香族第１アミン、並びに置換立体障害脂肪族又は脂環式及び芳香族第１アミンである。置換立体障害脂肪族又は脂環式及び芳香族第１アミンの場合には、脂肪族、脂環式又は芳香族基上の置換基は上記の通りである。適切な立体障害脂肪族又は脂環式アミンの非限定的な例としてはイソプロピルアミン、シクロヘキシルアミン、シクロオクチルアミン、イソブチルアミン及びシクロペンチルアミンが挙げられる。本発明の第１の態様では、本発明の方法で使用する第１の第２アミンの量は第１の第２アミンとポリアルデヒド中の−ＣＨＯのモル比として便宜的に表すことができ、即ち第１の第２アミンの量はポリアルデヒドの官能基密度により異なる。このようなモル比は約１：１〜約３０：１、好ましくは約１：１〜約２０：１、最適には約２：１〜約１０：１であり得る。生成されるポリ（第３アミン）はペンダント第３アミン官能基を含み、アルデヒド基のほぼ全部がアミノ化される。本発明の方法で使用される第１アミン又は第２の第２アミンの量は第１アミンとポリ（第３アミン）中の−ＣＨＯのモル比として便宜的に表すことができ、即ち第１アミン又は第２の第２アミンの量はポリ（第３アミン）中のアルデヒド基の官能基密度により異なる。このようなモル比は約１：１〜約３０：１、好ましくは約１：１〜約２０：１、最適には約２：１〜約１０：１であり得る。生成されるポリアミンはペンダント第２及び第３アミン官能基を含み、アルデヒド基のほぼ全部が還元的アミノ化される。本発明の第２の態様において、本発明の方法で使用される第１の第２アミンの量は第１の第２アミンとポリアルデヒド中の−ＣＨＯのモル比として便宜的に表すことができ、即ち第１の第２アミンの量はポリアルデヒドの官能基密度と還元的アミノ化すべきペンダントアルデヒド基の所望の百分率により異なる。このようなモル比は第１の第２アミンで還元的アミノ化すべきアルデヒド基の量に依存して典型的には約１：１である。あるいは、該モル比はポリアルデヒド中のアルデヒド基の合計量に依存して０．０１：１〜０．９９：１であり得る。本発明の方法で使用される第１アミン又は第２の第２アミンの量は、第１アミン又は第２の第２アミンとポリ（第３アミン）中の−ＣＨＯのモル比として便宜的に表すことができ、即ち第１アミン又は第２の第２アミンの量はポリ（第３アミン）中のアルデヒド基の官能基密度により異なる。このようなモル比は約１：１〜約３０：１、好ましくは約１：１〜約２０：１、最適には約２：１〜約１０：１であり得る。生成されるポリアミンはペンダントアミン官能基を含み、アルデヒド基のほぼ全部が還元的アミノ化される。本発明の第３の態様において本発明の方法で使用される合計アミンの量は、合計アミンとポリアルデヒド中の−ＣＨＯのモル比として便宜的に表すことができ、即ち合計アミンの量はポリアルデヒドの官能基密度により異なる。このようなモル比は約１：１〜約３０：１、好ましくは約１：１〜約２０：１、最適には約２：１〜約１０：１であり得る。本発明の方法で使用される第２アミン及び第１アミンの量は、第１アミンと第２アミンのモル比として便宜的に表すことができる。このようなモル比は（１）ポリアミン生成物上のペンダント第２及び第３アミン基の所望量と（２）第１及び第２アミンの相対反応性により異なる。当業者は本明細書の説明に基づいて制限された数の日常的実験で第１アミンと第２アミンの所望のモル比を容易に決定することができよう。生成されるポリアミンはペンダント第３及び第２アミン官能基を含み、アルデヒド基のほぼ全部が還元的アミノ化される。還元的アミノ化反応で使用される触媒は、還元的アミノ化中に炭素−炭素二重結合を水素化しないルテニウム含有イミン水素化触媒である。ルテニウム含有イミン水素化触媒は多種多様の形態をとり得る。例えば酸化ルテニウム（IV）水和物、無水二酸化ルテニウム（IV）及び四酸化ルテニウム（VIII）などのように酸化物形態でルテニウムを反応混合物に加えることができる。あるいは、塩化ルテニウム（III）水和物、臭化ルテニウム（III）、ヨウ化ルテニウム（III）、ヨウ化トリカルボニルルテニウム（III）、無水塩化ルテニウム（III）、硝酸ルテニウムなどのように無機酸の塩として加えてもよいし、例えば酢酸ルテニウム（III）、ナフテン酸ルテニウム（III）、吉草酸ルテニウムなどのように適切な有機カルボン酸の塩として加えてもよいし、ルテニウム（III）アセチルアセトナート（ｒｕｔｈｅｎｉｕｍ（III）ａｃｅｔｙｌａｃｅｔｏｎａｔｅ）などのようにカルボニル含有配位子を含むルテニウム錯体として加えてもよい。更に、カルボニル又は水素化ルテニウムカルボニル誘導体としてルテニウムを反応ゾーンに加えてもよい。この場合、適切な例としてはトリルテニウムドデカカルボニル及び他の水素化ルテニウムカルボニル［例えばＨ₂Ｒｕ₄（ＣＯ）₁₃及びＨ₄Ｒｕ₄（ＣＯ）₁₂］や、置換カルボニル種（例えば塩化トリカルボニルルテニウム（II）ダイマー［Ｒｕ（ＣＯ）₃Ｃｌ₂］₂）が挙げられる。好適なルテニウム含有イミン水素化触媒としてはルテニウムの酸化物、有機カルボン酸のルテニウム塩、及びルテニウムカルボニル又は水素化ルテニウムカルボニル誘導体が挙げられる。このうちでは二酸化ルテニウム（IV）水和物、四酸化ルテニウム、無水酸化ルテニウム（IV）、酢酸ルテニウム、ルテニウム（III）アセチルアセトナート及びトリルテニウムドデカカルボニルが特に好適である。最適なルテニウム含有イミン水素化触媒はトリルテニウムドデカカルボニル（Ｒｕ₃（ＣＯ）₁₂）である。ルテニウム含有イミン水素化触媒を使用する場合には、還元的アミノ化は水素雰囲気下で実施される。還元的アミノ化は場合により、一酸化炭素と水素の比を約０．１５：１未満、好ましくは約０．１：１未満、最適には約０．０５：１未満とした水素及び一酸化炭素雰囲気下で実施され得る。還元的アミノ化中の水素又は水素／一酸化炭素の圧力は約１５０ｐｓｉｇ〜約１０００ｐｓｉｇ、好ましくは約２００ｐｓｉｇ〜約１０００ｐｓｉｇである。還元的アミノ化の温度は約１１０℃〜約２００℃、好ましくは約１２０℃〜約１５０℃である。還元的アミノ化で使用されるアルカリ金属ホウ水素化物は好ましくはホウ水素化ナトリウム又はリチウム、最適にはホウ水素化ナトリウムである。適切なアルカリ金属ホウ水素化物の非限定的な例としては、ＮａＢＨ（Ｏ₂ＣＣＨ₃）₃、ＮａＢＨ₃ＣＮ、ＮａＢＨ₄、ＬｉＢＨ₄及びその混合物を挙げることができる。一般に好適なアルカリ金属ホウ水素化物はその効力と良好な結果が得られることからＮａＢＨ（Ｏ₂ＣＣＨ₃）₃及びＮａＢＨ₃ＣＮである。還元的アミノ化は典型的には適切な溶剤系の存在下で実施される。適切な溶剤系の非限定的な例としてはトルエン、キシレン、ジメチルホルムアミド（ＤＭＦ）とアルカン又はシクロアルカンの混合物（例えばＤＭＦ／シクロヘキサン）、エーテル類（例えばテトラヒドロフラン）、塩素化炭化水素（例えばジクロロエタン）等、及びその混合物が挙げられる。ルテニウム含有イミン水素化触媒を使用する場合に一般に好適な溶剤系はＤＭＦとシクロヘキサンの混合物である。アルカリ金属ホウ水素化物を使用する場合に一般に好適な溶剤系はテトラヒドロフランである。本発明の方法により製造されるポリアミンは任意の慣用回収方法により回収することができる。このような回収方法の例は下記実施例中に記載する。実施例実施例１本実施例はポリブタジエンをベースとするポリアルデヒドの製造を例示する。ポリブタジエン（ＲｅｖｅｒｔｅｘＮ４５００；４５％ビニルＭＮ＝４５００）の１０００．１９ｇサンプルをトルエン１３００ｍＬに溶かした。Ｎ₂雰囲気下でこのポリマー溶液を１ガロン容オートクレーブに注いだ。次いでトリフェニルホスフィン６．９ｇとヒドリドカルボニルトリス（トリフェニルホスフィン）ロジウム（Ｉ）０．４２ｇをＮ₂雰囲気下でオートクレーブに加えた。オートクレーブを密閉し、オートクレーブを２００ｐｓｉのＮ₂で加圧した後、Ｎ₂ガスを排気する（ｖｅｎｔ）ことによりＮ₂で更に脱気した。次にオートクレーブを４００ｐｓｉのＮ₂下に８０℃まで加熱した。Ｎ₂を除去後、オートクレーブに８０℃で１６０ｐｓｉの１：１ＣＯ／Ｈ₂を充填した。目盛付き容器から２４８７ｐｓｉｇの１：１ＣＯ／Ｈ₂が反応するまで反応混合物を１０００ｒｐｍで撹拌した。オートクレーブを排気後、ポリマー生成物を取り出した。オートクレーブをトルエン１００ｍＬで洗浄し、洗浄液をポリマー生成物に加えた。生成物溶液をロータリーエバポレーションにより濃縮した。このポリマー溶液を次に、４：１メタノール／水を含む溶液にゆっくりと滴下した。溶液を２相に分離させ、上相をデカントした。底部のポリマー相をトルエンに溶かし、上記沈澱の手順を繰り返した。この手順からポリマー生成物を単離した。ＫＢｒプレート上のポリマー生成物の薄膜の赤外スペクトルは、１７３０ｃｍ^-1におけるアルデヒド吸収を示した。¹ＨＮＭＲはＰ（ｂｄ）ポリマー中の二重結合の３２．６７％がヒドロホルミル化されたことを示した。アルデヒドプロトンをポリマー主鎖中のオレフィン性ピークに対して統合（ｉｎｔｅｇｒａｔｅ）し、ヒドロホルミル化されたブタジエン単位の百分率を計算する。選択的¹ＨＮＭＲ共鳴：δ９．７５メジャー（＞９０％）；９．５５及び９．６５マイナー，アルデヒド；４．８−５．１，ｍ，ＣＨ₂ ＝Ｃ，５．１５−５．６５，ｍ。実施例２本実施例は実施例１で製造したポリアルデヒドを使用するポリ（第３アミン）の製造を例示する。実施例１で製造したポリアルデヒドのトルエン溶液（１）を減圧濃縮した。次いでＤＭＦ９０９ｍＬ中の３０６ｇの生成物１、シクロヘキサン５７３ｍＬ、ジメチルアミン３１８ｇ及びルテニウムカルボニル３．１ｇを１ガロン容オートクレーブに仕込んだ。オートクレーブを密閉し、１００ｐｓｉｇのＣＯ／Ｈ₂でパージした。オートクレーブに１００ｐｓｉｇのＣＯ／Ｈ₂と９００ｐｓｉｇのＨ₂を充填し、１０００ｒｐｍの速度で撹拌しながら１２０℃まで加熱した。反応温度が約１００℃に達するとガス取込が開始した。ガス取込が停止するまで（約４時間）反応を進行させた。室温まで冷却後、オートクレーブの内容物を取り出し、３個の２Ｌ容分液漏斗に入れ、相分離させた。漏斗の各々で合計容量レベルを記録した。下層の赤みがかった茶色のＤＭＦ層を取り出して廃棄した。ＤＭＦ３００ｍＬを各分液漏斗に加え、シクロヘキサンも加えてフラスコ中の液体レベルを元の容量まで増加させた。漏斗を震盪し、シクロヘキサン層をＤＭＦで抽出し、分離手順を繰り返した。ＤＭＦ抽出手順を合計３回行った。シクロヘキサン層を中位の多孔度のガラス−フリットブフナー漏斗（ｇｌａｓｓ−ｆｒｉｔｔｅｄｂｕｃｈｎｅｒｆｕｎｎｅｌ）で濾過し、トルエンを加えて５０℃で回転蒸発（ｒｏｔｏｖａｐｐｅｄ）させ、残留ＤＭＦを除去した。ポリマーを真空管路（ｖａｃｕｕｍｌｉｎｅ）で２時間乾燥した。ｄ₄ −酢酸中の¹ＨＮＭＲはアルデヒドが第３アミン基に完全に変換したことを示した。次いでアミノ化ポリマーを暗所でトルエン中で保存した。選択プロトンＮＭＲ共鳴（ｓｅｌｅｃｔｅｄｐｒｏｔｏｎＮＭＲｒｅｓｏｎａｎｃｅｓ）（ＣＤ₃ＣＯ₂Ｄ）：オレフィン性ピーク：δ５．４５−５．１，ｍ，及び４．９−４．６５，ｍ，ＣＨ₂ ＝Ｃ；δ２．６５，ｓ，（ＣＨ₃ ）₂ＮＨ＋；δ２．９，ｓ，ポリマー−ＣＨ₂ ＮＨ（ＣＨ₃）₂ 。アルデヒドピークは検出されなかった。実施例３本実施例は実施例１の方法により製造したポリアルデヒドを使用するポリ（第３アミン）の別の製造を例示する。実施例１の方法により製造し、ヒドロホルミル化したポリブタジエン中に３３％の炭素−炭素二重結合をもつポリアルデヒド（６３．１４ｇ）を４Å分子篩乾燥トルエン１００ｍＬとメタノール２０ｍＬに溶かし、温度計、添加漏斗及び磁気撹拌棒を備える２Ｌ容三頚丸底フラスコにこの溶液を入れた。溶液を更にＴＨＦ５００ｍＬ及びメタノール４０ｍＬで希釈した。Ｎ₂下で５℃まで冷却後、ジメチルアミン（５０ｇ）を撹拌下に加えた。１５分後にジオキサン溶液中の４．５ＭＨＣｌ８５．８ｍＬを添加漏斗により溶液にゆっくりと加えた。最後にシアノホウ水素化ナトリウム１７ｇを漏斗でゆっくりと加え、フラスコにＴＨＦ２０ｍＬを濯ぎ入れた。溶液を４０時間撹拌し、室温までゆっくりと昇温させた。ポリマー溶液に水６０ｍＬを加えて１時間撹拌した後、濾過した。濾液を２００ｍＬ容量まで濃縮し、２時間静置した後、上部ポリマー相をメタノール４００ｍＬと水１００ｍＬの混合物にゆっくりと滴下した。底部ポリマー相をデカントし、分離した。沈殿手順を繰り返した。ポリ（第３アミン）６４．６ｇが単離された。元素分析（実測値）：％Ｃ８０．６２，％Ｈ１１．６６，％Ｎ６．６２。ｄ₄−酢酸中の¹ＨＮＭＲはアルデヒドが第３アミン基に完全に変換したことを示した。選択プロトンＮＭＲ共鳴（ＣＤ₃ＣＯ₂Ｄ）：オレフィン性ピーク：δ５．４５−５．１，ｍ，及び４．９−４．６５，ｍ，ＣＨ₂ ＝Ｃ；δ２．６５，ｓ，（ＣＨ₃ ）₂ＮＨ＋；δ２．９，ｓ，ポリマー−ＣＨ₂ ＮＨ（ＣＨ₃）₂。アルデヒドピークは検出されなかった。実施例４本実施例は制御された量のアルデヒド基をもつポリブタジエンをベースとするポリ（第３アミン）の製造を例示する。実施例２で製造され、ジメチルアミノ基で官能化された炭素−炭素二重結合３２．６７％を含むポリブタジエンをベースとするポリ（第３アミン）（３０ｇ）を３００ｍＬ容Ｐａｒｒ反応器でトルエン１８０ｍＬに溶かした。ＨＲｈ（ＣＯ）（ＰＰｈ₃）₃（０．００９ｇ）及びＰＰｈ₃（０．０９ｇ）を反応器に加えた。反応器を密閉した後、２５ｐｓｉｇの窒素で３回パージした。反応器を３ｐｓｉｇの窒素下で１００℃まで加熱した。反応器温度が１００℃で安定したら反応器に６００ｐｓｉｇの合成ガス（Ｈ₂／ＣＯ１：１）を充填した。目盛付き容器を用いてガス取込をモニターし、所望量のガスが取り込まれたら反応器を冷却及び排気し、反応を終了した。次に反応混合物を反応器から取り出した。小サンプルを減圧乾燥し、¹ＨＮＭＲにより分析した。ＮＭＲによると、出発ポリ（第３アミン）中の二重結合の４３．０７％又は最初の二重結合の２９．００％がアルデヒド基で官能化されたことが判明した。実施例５本実施例は実施例４で製造した制御された量のアルデヒド基を含むポリ（第３アミン）を使用するポリブタジエンをベースとするポリアミンの製造を例示する。実施例３で製造した制御された量のアルデヒド基を含むポリ（第３アミン）をロータリーエバポレーターで濃縮し、存在するトルエンのほぼ全部を除去した。次にポリマーをジメチルホルムアミド（ＤＭＦ）６０ｍＬとシクロヘキサン６０ｍＬの混合物に溶かした。Ｒｕ₃（ＣＯ）₁₂（０．１００ｇ）を加え、イソプロピルアミン（３当量／ＣＨＯ；０．３１８モル；１８．８０ｇ）を加えた。反応器を密閉し、Ｈ₂／ＣＯ（１：１）で６回パージした。反応器にＨ₂／ＣＯ（１：１）を６７ｐｓｉｇまで充填した後、全圧４１２ｐｓｉｇまでＨ₂を充填した。反応器を１２０℃まで加熱した。反応器の温度が安定したら反応器に６００ｐｓｉｇまでＨ₂を充填し、一晩反応させた。反応器を冷却し、排気した。反応混合物をガラスウールで濾過した後、２５０ｍＬ分液漏斗に入れ、相分離させた。シクロヘキサン層をＤＭＦ６０ｍＬで３回洗浄した後、シクロヘキサン層を分離し、全溶剤を除去した。次にポリマーをトルエンに再溶解した。サンプルを減圧乾燥して分析した。ｄ₄−酢酸中の¹ＨＮＭＲはポリマーに結合したジメチルアミノ及びイソプロピルアミノ基の特徴的ピークを示した。ＮＭＲでは未反応アルデヒドは検出されなかった。元素分析：計算値：Ｃ７８．０２％，Ｈ１２．８４％，Ｎ９．１４％；実測値：Ｃ７７．７９％，Ｈ１２．９８％，Ｎ９．０４％。以上の結果は、ポリマーが所望通り第２及び第３アミン基で選択的に官能化されたことを示す。最終生成物は安定な可溶性ポリマーであった。実施例６本実施例は、第３アミン基の前に第２アミン基を加えた場合には制御された量の第２及び第３アミン基を含む安定した可溶性ポリアミンが生成されないことを立証する比較例である。ポリアルデヒド：ポリブタジエン（２５．０ｇ，Ａｌｄｒｉｃｈ２０，０５０−６；４５００Ｍ．Ｎ．；４５％ビニル；５５％シス及びトランス）を３００ｍＬ容Ｐａｒｒ反応器に仕込んだ。トリフェニルホスフィン（ＰＰｈ₃；０．３０ｇ）を反応器に加え、更にＨＲｈ（ＣＯ）（ＰＰｈ₃）₃（０．０３ｇ）も反応器に加えた。反応体をトルエン１５０ｍＬに溶かし、反応器を閉じた。反応器を撹拌しながら２５ｐｓｉｇの窒素でパージした後、２ｐｓｉｇの窒素下で反応器を１００℃まで加熱した。反応器の温度が安定したら反応器に２００ｐｓｉｇのＨ₂／ＣＯ（合成ガス）を充填した。目盛付き容器で圧力降下を観察することによりガス取込をモニターした。適量のガスが取込まれたら、反応混合物を迅速に冷却して合成ガスを排気することにより反応を停止した。次に反応混合物を窒素（３×２５ｐｓｉｇ）でパージし、反応器から取り出した。溶液をロータリーエバポレーションにより濃縮した。ポリマーをメタノール／水（４：１）でトルエンから沈殿分離した。溶剤をデカントし、ポリマーをトルエンに再溶解し、再びメタノール／水（４：１）で沈殿させた。ポリマーをトルエンに再溶解し、サンプルを乾燥して¹ ＨＮＭＲ分析した。¹ＨＮＭＲはアルデヒド基による３３．８５％の官能化を示した。ポリ第２アミン：ポリアルデヒド溶液のアリコート（１２．６９ｇ溶液；５．０ｇポリマー）を分取し、ロータリーエバポレーションによりトルエンを除去した。ポリマーをジメチルホルムアミド（ＤＭＦ）に溶かし、ＤＭＦが合計７５ｍＬとなるように３００ｍＬ容Ｐａｒｒ反応器に移した。ルテニウムカルボニル（Ｒｕ₃（ＣＯ）₁₂ ；０．０１ｇ）とイソプロピルアミン（３．０当量；６．７４ｇ）を反応器に加えた。シクロヘキサン（７５ｍＬ）を反応器に加え、反応器を閉じた。反応器を６０ｐｓｉｇの合成ガス（Ｈ₂／ＣＯ；１：１）で２回パージした。反応器に６０ｐｓｉｇの合成ガスを充填した後、全圧４００ｐｓｉｇまで水素を充填した。入口バルブを閉じて反応器を１２０℃まで加熱した。反応を７時間進行させた処、この時点でガス取込は停止していた。反応器を冷却及び排気した後、２５ｐｓｉｇの窒素で３回パージした。反応混合物を反応器から取り出し、５００ｍＬ容分液漏斗で相分離させた。相分離が完了したら下部ＤＭＦ層を除去した。ＤＭＦ（７５ｍＬ）とシクロヘキサン（３０ｍＬ）をポリマー溶液に加え、混合後、相分離させてシクロヘキサン層の第２回目の抽出を行った。ＤＭＦ層を除去し、シクロヘキサン層をロータリーエバポレーターで乾燥した。ポリマーをトルエンに再溶解した。ポリマーのアリコートの¹ＨＮＭＲはポリマー上でアルデヒド基がイソプロピルアミン基に変換したことを示した。ポリ第２アミン−アルデヒド：イソプロピルアミノ置換ポリブタジエンをトルエンに溶かし、１００ｍＬ容Ｐａｒｒ反応器に仕込んだ。トリフェニルホスフィン（１．５ｇ）とＨＲｈ（ＣＯ）（ＰＰｈ₃）₃（０．０３ｇ）を反応器に加え、少量のトルエン（〜５ｍＬ）で洗浄した。反応器を閉じ、２５ｐｓｉｇの窒素で３回パージした。次に反応器を２ｐｓｉｇの窒素下で１００℃まで加熱した。反応器の温度が平衡したら２００ｐｓｉｇの合成ガスを充填した。目盛付き容器から５５ｐｓｉｇのガスが取込まれるまで反応を進行させた。反応器を冷却及び排気した後、２５ｐｓｉｇの窒素で３回パージした。反応混合物を反応器から取り出し、びんに入れて窒素でスパージした後、冷凍庫で保存した。溶液のアリコートを真空管路で乾燥し、¹ＨＮＭＲ分析した。ポリマー上に活性ホルミル基と第２アミン基が存在するので、アリコートを非常に短時間（３０秒）乾燥し、トルエンの大部分を除去した。長時間乾燥したアリコートはゲル化し、有機溶剤に溶けなかった。次にポリマーをＣＤＣｌ₃に溶かした。ポリマーの¹ ＨＮＭＲは、ポリマー中の最初の二重結合の１７．４２％がヒドロホルミル化されたことを示した。ポリ第２アミン−アルデヒドの還元的アミノ化ポリ第２アミン−アルデヒドをトルエンに溶かし、３００ｍＬ容Ｐａｒｒ反応器に入れた。ルテニウムカルボニル（Ｒｕ₃（ＣＯ）₁₂；０．１００ｇ）を反応器に加えた。自重を計量した別のフラスコにＤＭＦ５０ｍＬを入れてゴム栓をし、十分なジメチルアミン（１．６８ｇ，３当量）がＤＭＦに溶けるまでジメチルアミンをバブリングした。ジメチルアミン溶液を反応器に加え、反応器を閉じた。反応器を１００ｐｓｉｇの合成ガス（１：１Ｈ₂／ＣＯ）で２回パージした後、６０ｐｓｉｇまで合成ガスを充填した。次に反応器に全圧４００ｐｓｉｇまで水素を充填した後、入口バルブを閉じて反応器を１２０℃まで加熱した。反応を１７時間進行させた処、この時点でガス取込は停止していた。反応器を冷却及び排気した後、２５ｐｓｉｇの窒素で３回パージした。反応混合物を反応器から取り出した。トルエンをロータリーエバポレーションにより溶液から除去すると、この時点でポリマーはゲル化し、最早有機溶剤に溶けなかった。この方法では第２及び第３アミン基の両者を含む安定な可溶性ポリマーは製造されなかった。Detailed Description of the Invention Functional group density control polyamine and method for producing the same Background of the Invention The present invention is directed to functional group density controlled polyamines containing olefinic unsaturation (contro for led functional density polyamines) Related. In one aspect, the invention features a controlled amount of pendant. ) Manufacture of functional group density controlled polyamines having tertiary amine and pendant secondary amine groups Regarding construction. In another aspect, the invention provides a controlled amount of two different pendants. To the production of functional group density controlled polyamines having tertiary amine groups. Yet another aspect In the present invention, the present invention relates to carbon-carbon double bonds in starting polymers containing olefinic unsaturation. Functional Group Density Controlled Polyamine Containing Olefinic Unsaturation by Selective Reaction of Bonding Related to manufacturing. Reacting an olefin with hydrogen, carbon monoxide and a primary or secondary amine to yield an amine The principle of manufacturing is known. A variety of embodiments that embody this principle using a variety of catalysts. Method reported Have been. Such a method is generally called an aminomethylation reaction. J. Org. Chem. , 47, 445 (1982) by Jachimo. wicz et al. devise an efficient and general one-step conversion of olefins to amines The various approaches used in the trial are disclosed. Pentacarbonyl as a catalyst Iron, rhodium oxide, ruthenium / iron carbonyl and iridium catalysts are listed I have. U.S. Pat. No. 4,297,481 discloses at least two labiles. e) a monomeric nitrogen compound in which hydrogen is attached to the nitrogen atom, at least two olefins Monomeric hydrocarbon compounds containing benzene groups, carbon monoxide and water in catalytic amounts of rhodium The amino / amide nitrogen is brought into contact with the polymer backbone ( a method for forming a polymeric polyamine / amide containing backbone) is disclosed. I have. This invention describes the use of ammonia or primary amines Polymers with only secondary amine groups have not been produced, and pendant secondary and secondary We have not produced polymers that can control the amount of triamine groups. Pendant amine and The production of polymers having amide groups is described in US Pat. 965. These polymers are polymeric polyolefins, monoxides. Manufactured from carbon, water, and nitrogen compounds such as ammonia and primary or secondary amines You. Here too, rhodium or rhodium-containing compounds are used as catalysts. I However, the polymers described in this invention have a low amine uptake and start with primary amines. When used as a material, the tertiary amine group occupies the majority, and the pendant secondary and secondary amine groups are used. It is not possible to control the amount of triamine groups. U.S. Pat. No. 4,503,217 discloses a catalyst system containing a ruthenium-containing catalyst, A dimethylformol that provides a two-phase liquid product for easy separation of the polyamines. In the presence of a mixed amido-alkane solvent, polybutadiene, ammonia and Teaches how to make polymeric polyamines from secondary amines, carbon monoxide and hydrogen. Is shown. When using primary amines in this invention, only vinyl groups are functionalized. The yield of amine-containing polymer is low and the resulting polymer is insoluble in organic solvents. It is. U.S. Pat. No. 4,657,984 discloses ruthenium or rhodium phosphite as a catalyst. Polymer from carbon monoxide, hydrogen, polymeric olefins and secondary amines using Poly (3rd Min) is disclosed. This patent uses these specific catalysts. This facilitates the reaction and thus the functionalization of the internal and vinyl olefin groups. I said that. As described above, there are various conventional techniques for producing the polymer second and third polyamines. Reaction of vinyl olefin with internal olefin under various conditions using various catalysts It teaches the resulting aminomethylation reaction. However, conventional aminomethylation techniques The technique depends on the degree of functionalization of the polyaldehyde or the polyamine produced from the polyaldehyde. No teaching on how to control functional group density, especially the amount of various amine pendant groups Since these reactions have not been carried out, these reactions are carried out by hydroformylation and reductive amination. It is significantly different from Kens. Using milder reaction conditions, the result was a controlled amount of pendant tertiary Min and pendant secondary amine groups, or controlled amounts of two different pendants. A polymer having a high density of functional groups containing a tertiary amine group is produced, and a polymer soluble in an organic solvent is produced. Functional group density control polyamid containing residual reactive carbon-carbon double bonds to form mer It would be highly desirable if a method of manufacturing a battery could be realized. The polyamines produced by the method of the present invention are useful in rubber chemicals such as Polymer-bonded accelerator that does not release dangerous volatiles during curing, separate from one component Co-activators that cannot be transferred to the components of Polymer-bonded antioxidants with a significantly lower tendency to leach from rubber products (eg tires) Used as an agent and / or an antiozonant. Manufactured by the method of the present invention A controlled amount of pendant tertiary amine groups and pendant secondary amine groups. Liamines are also useful in urethane / urea materials, coatings, adhesives and sealants And when the polyamine contains a pendant secondary amine group, it favors a tertiary amine. It is also useful for the construction of three-dimensional networks through unusable bonds. Summary of the invention One object of the present invention is the preparation of functional group density controlled polyamines containing olefinic unsaturation. It is to provide a manufacturing method. Another object of the invention is the controlled amount of pendants. A tertiary and secondary amine group or a controlled amount of two different tertiary amine groups and It does not substantially contain a tertiary amine group derived from a pendant secondary amine group, Of functional group density soluble in the agent Uses efficient, commercially viable, mild reaction conditions that produce high polymers Of functional group density-controlled polyamine containing residual reactive carbon-carbon double bond Is to provide a method. Still another object of the present invention is to set a curing accelerator and a polymer auxiliary. For use in rubber chemical applications such as activators and antioxidants / antiozonants It is an object of the present invention to provide a method for producing a functional group density-controlled polyamine. In accordance with the present invention, a controlled amount of pendant tertiary amine groups and a controlled amount of peptide are provided. A method for the preparation of secondary amines or polyamines containing different tertiary amine groups is provided. The method comprises: (1) hydrogen and a ruthenium-containing imine hydrogenation catalyst or (2) Lucali metal borohydride ) In the presence of a controlled amount of pendant aldehyde groups under reductive amination conditions. And a polyaldehyde containing a reactive carbon-carbon double bond is contacted with a primary secondary amine. The ratio of the tertiary amine group to the reactive carbon-carbon double bond is Poly (tertiary amine) that is substantially equal to the ratio of dehydrate groups to reactive carbon-carbon double bonds Under conditions of hydroformylation in the presence of a hydroformylation catalyst. Contains reactive carbon-carbon double bonds The poly (tertiary amine) is contacted with carbon monoxide and hydrogen to produce a controlled amount of alcohol. A step for producing a poly (tertiary amine) containing a dehydration group and a reactive carbon-carbon double bond Floor, and (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal A controlled amount of aldehyde groups under reductive amination conditions in the presence of hydride and A poly (tertiary amine) containing a reactive carbon-carbon double bond is used as a primary amine or a secondary amine. A secondary amine group or a third derivative derived from a second secondary amine by reacting with a secondary amine The ratio of amine groups and reactive carbon-carbon double bonds is controlled to a controlled amount of aldehyde groups and Aldehyde group in poly (tertiary amine) containing reactive carbon-carbon double bond and reactive carbon Producing a polyamine substantially equal to the ratio of elementary-carbon double bonds, Poly (3rd group) containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. Reductive amination of (amine) with a primary amine in the presence of an alkali metal borohydride. When practiced with, primary amines are sterically hindered aliphatic or cycloaliphatic primary amines. Min or an aromatic primary amine. In one embodiment, the reductive amination is carbon monoxide. It is carried out in the presence of the element. In another aspect, the polyaldehyde is olefinic. Hydroformyl polymers containing unsaturation It is produced by contacting with carbon monoxide and hydrogen in the presence of a hydrogenation catalyst. Further In another embodiment, a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. The amount of aldehyde groups in the polyaldehyde or poly (tertiary amine) containing It is controlled by controlling the consumption of carbon monoxide and hydrogen during the formylation. Further in accordance with the present invention, a controlled amount of pendant tertiary amine groups and a controlled amount of Of pendant secondary amines or polyamines containing different tertiary amine groups And a method of (1) hydrogen- and ruthenium-containing imine hydrogenation catalyst or (2 ) A controlled amount of reductive amination conditions in the presence of alkali metal borohydride A polyaldehyde containing a pendant aldehyde group and a reactive carbon-carbon double bond , A first amount of a first amount which depends on the percentage of pendant aldehyde groups to be reductively aminated. Contacting with a secondary amine to provide pendant tertiary amine groups in the poly (tertiary amine) and The ratio of the sum of pendant aldehyde groups and the reactive carbon-carbon double bond in polyaldedo Of the pendant aldehyde group and the reactive carbon-carbon double bond of As controlled amount of pendant tertiary amine groups, controlled amount of pendant Aldehi And a poly (tertiary amine) containing a controlled amount of reactive carbon-carbon double bonds. The step of forming, and (1) hydrogen and a ruthenium-containing imine hydrogenation catalyst or (2) al Poly (tertiary amine) was prepared under reductive amination conditions in the presence of potassium metal borohydride. Contact with a primary amine or a secondary secondary amine to form a secondary amine group or secondary secondary amine. The ratio of the amine-derived tertiary amine group to the reactive carbon-carbon double bond is poly (tertiary Amine) and the reactive carbon-carbon double bond ratio in the amine. Forming a reamine, provided that the reductive amination is alkali metal borohydride. When carried out with a primary amine in the presence of a halide, the primary amine is sterically hindered. It is an aliphatic or alicyclic primary amine or an aromatic primary amine. In one aspect The reductive amination is carried out in the presence of carbon monoxide. In another embodiment, poly Aldehydes are the catalysts for hydroformylation of polymers containing olefinic unsaturation. It is produced by contacting with carbon monoxide and hydrogen under the atmosphere. In yet another aspect , Polyaldehyde functional group density, that is, a polymer containing olefinic unsaturation The molar percentage of carbon-carbon double bonds hydroformylated to aldehyde groups in , Carbon monoxide during hydroformylation And controlled by controlling the consumption of hydrogen. Further in accordance with the present invention, a controlled amount of pendant tertiary amine groups and a controlled amount of A method of making a polyamine comprising pendant secondary amine groups of is provided, the method comprising: (1) Hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal borohydride Controlled amount of pendant aldehyde groups in the presence of halides under reductive amination conditions And a polyaldehyde containing a carbon-carbon double bond, a primary secondary amine and a primary amine. Of the tertiary amine group and the secondary amine group and the reactive carbon-carbon double The bond ratio determines the ratio of the aldehyde groups in the polyaldehyde to the reactive carbon-carbon double bond. Comprising producing substantially equal poly (second / tertiary amine), the first secondary amine The molar ratio of the amine to the primary amine depends on the relative reactivity of the primary and secondary amines and the primary amine. Dependent on the desired controlled amount of tertiary amine and pendant secondary amine groups. , Provided that the reductive amination is carried out in the presence of an alkali metal borohydride. Is a sterically hindered aliphatic or alicyclic primary amine or aromatic primary amine. It is. In one embodiment, the reductive amination is carried out in the presence of carbon monoxide. . In another embodiment, the polyaldehyde is hydroformylated. Contacting polymers containing olefinic unsaturation with carbon monoxide and hydrogen in the presence of catalysts It is generated by In yet another embodiment, the alkyl in the polyaldehyde is The amount of dehydration group controls the consumption of carbon monoxide and hydrogen during hydroformylation Controlled by. Further in accordance with the present invention, olefinic unsaturation with a reactive carbon-carbon double bond Containing repeating units derived from repeating units of the containing polymer and olefinic unsaturation The same polymer and hydroformylated to give pendant secondary amines and tertiary amines. Derived from recurring units of a polymer that is reductively aminated to produce a phenyl group A polyamine comprising repeating units is provided, wherein the polyamine has a functional group density of 2 to about 90. Mol%, and the number of repeating units having a pendant tertiary amine group is And about 5 to about 95% of the total number of repeating units having a secondary amine group, provided that the pendant The number of repeating units with a secondary amine group and repeating units with a pendant tertiary amine group is A repeating unit containing a reactive carbon-carbon double bond and a pendant secondary and tertiary amine group Each of which is at least 1% of the total number of repeating units containing. Further according to the invention, having a reactive carbon-carbon double bond A repeating unit derived from a repeating unit of a polymer containing olefinic unsaturation; The same polymer containing finic unsaturation and hydroformylated to give two different Polymers Reductively Aminated to Form Repeating Units Having a Tertiary Amine Group A polyamine containing a repeating unit derived from a repeating unit of The functional group density of the amine is 2 to about 90 mol%, and the group derived from one of the secondary amines is The number of repeating units with a pendant tertiary amine group depends on the number of repeating units with a pendant tertiary amine group. About 5 to about 95% of the total number of units, provided that it is derived from the primary secondary amine The number of repeating units having pendant tertiary amine groups and derived from a second secondary amine The number of repeating units having a pendant tertiary amine group is determined by the number of reactive carbon-carbon double bonds. With olefinic unsaturation having a pendant and a pendant tertiary amine group Each is at least 1% of the sum of the numbers of units. Detailed description of the invention The first aspect of the present invention is a controlled amount of pendant tertiary amine groups with a controlled amount. For the production of polyamines containing a quantity of pendant secondary amines or different tertiary amine groups Regarding the method, the method comprises: (a) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst Medium or (2) control under reductive amination conditions in the presence of alkali metal borohydride Polya containing a pendant amount of pendant aldehyde groups and a reactive carbon-carbon double bond. The aldehyde is contacted with a primary secondary amine to react with a tertiary amine group and a reactive carbon-carbon diamine. The ratio of heavy bonds is the ratio of reactive carbon-carbon double bonds to the aldehyde groups in polyaldehyde. Producing a poly (tertiary amine) substantially equal to: (b) hydroformyl Of compounds containing a reactive carbon-carbon double bond under hydroformylation conditions in the presence of a hydrogenation catalyst. Contacting carbon monoxide and hydrogen to a controlled amount of aldehyde. Forming a poly (tertiary amine) containing a pendant group and a reactive carbon-carbon double bond; , (C) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal Controlled amount of aldehyde groups under reductive amination conditions in the presence of borohydride And a poly (tertiary amine) containing a reactive carbon-carbon double bond as a primary amine or a secondary amine. A secondary amine group or a secondary amine derived from a secondary secondary amine is reacted with the secondary amine. 3 amine groups and reactive carbon-carbon double bond ratios in controlled amounts of aldehyde groups and Reactivity with aldehyde groups in poly (tertiary amine) containing reactive carbon-carbon double bond The carbon-carbon double bond ratio is substantially Producing an equivalent polyamine, provided that the reductive amination of (c) is When performed with a primary amine in the presence of a remetal borohydride, the primary amine is used. Min is a sterically hindered aliphatic or cycloaliphatic primary amine or aromatic primary amine. According to the method of the first aspect of the present invention, the polyaldehyde of (a) is olefinic. Polymers containing unsaturation were treated with carbon monoxide and hydrogen in the presence of hydroformylation catalysts. It is generated by bringing them into contact. In addition, the reductive amination involves hydrogen and ruthenium. When carried out in the presence of an imine-containing hydrogenation catalyst, the reducing reductive of (a) or (c) The amination can optionally be carried out in the presence of carbon monoxide. During reductive amination When carbon monoxide is present, the molar ratio of carbon monoxide to hydrogen is less than about 0.15: 1, Preferably less than about 0.1: 1, optimally less than about 0.05: 1. A second aspect of the invention is a controlled amount of pendant tertiary amine groups and a controlled amount of Of pendant secondary amines or polyamines containing different tertiary amine groups (A) (1) hydrogen and a ruthenium-containing imine hydrogenation catalyst, or 2) Reductive in the presence of alkali metal borohydride Controlled amounts of pendant aldehyde groups and reactive carbon-carbon under amination conditions Pendant aldehydes for reductive amination of polyaldehydes containing double bonds A poly (tertiary amine) in contact with a primary secondary amine in an amount dependent on the percentage of the groups. Of pendant tertiary amine groups and pendant aldehyde groups in and reactive carbon-carbon The ratio of elementary double bonds is reactive carbon-carbon with pendant aldehyde groups in polyaldedo A controlled amount of pendant tertiary amino acid such that the ratio of double bonds is substantially equal. Group, a controlled amount of pendant aldehyde groups and a controlled amount of reactive carbon- Generating a poly (tertiary amine) containing a carbon double bond, and (b) (1) hydrogen In the presence of ruthenium-containing imine hydrogenation catalyst or (2) alkali metal borohydride A poly (tertiary amine) of (a) under reductive amination conditions to a primary amine or a secondary amine A secondary amine group or a secondary amine derived from a secondary secondary amine in contact with the secondary amine. In the poly (tertiary amine) with a ratio of triamine groups to reactive carbon-carbon double bonds (a) Produces a polyamine that is substantially equal to the ratio of aldehyde groups to reactive carbon-carbon double bonds. And the reductive amination of (b) is an alkali metal borohydride. Carried out with a primary amine in the presence of Primary amines are sterically hindered aliphatic or cycloaliphatic primary amines or aromas. It is a group 1 primary amine. According to the method of the second aspect of the invention, the polyaldehyde is olefinically unsaturated. Of a polymer containing carbon with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst. It is generated by In addition, the reductive amination of (a) or (b) with hydrogen When carried out in the presence of a ruthenium-containing imine hydrogenation catalyst, the reductive amino The conversion can optionally be carried out in the presence of carbon monoxide. Monoxide during reductive amination When carbon is present, the molar ratio of carbon monoxide to hydrogen is less than about 0.15: 1, preferably Or less than about 0.1: 1, optimally less than about 0.05: 1. A third aspect of the invention is a controlled amount of pendant tertiary amine groups and a controlled amount of And a method for producing a polyamine containing pendant secondary amine groups of ) (1) Hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal borate Controlled amounts of pendant aldehydes under reductive amination conditions in the presence of dichloride A polyaldehyde containing a group and a carbon-carbon double bond, a primary secondary amine and a primary amine And react with the sum of the number of tertiary amine groups and secondary amine groups. The ratio of reactive carbon-carbon double bonds to the aldehyde groups in polyaldehyde reacts with reactive carbon-carbon. Comprising producing poly (second / tertiary amine) substantially equal to the ratio of elementary double bonds. However, the molar ratio of the first secondary amine and the primary amine is the same as that of the primary secondary amine and the primary amine. Desirable control of relative reactivity and pendant tertiary amine and pendant secondary amine groups Dependent on the amount used, but reductive amination in the presence of alkali metal borohydride When practiced, the primary amine is a sterically hindered aliphatic or cycloaliphatic primary amine or Is an aromatic primary amine. According to the method of the third aspect of the present invention, the polyaldehyde exhibits olefinic unsaturation. Contacting the containing polymer with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst. It is generated by In addition, reductive amination can be carried out using hydrogen and ruthenium-containing imines. When carried out in the presence of a hydrogenation catalyst, the reductive amination is optionally a monoxide. It can be carried out in the presence of carbon. If carbon monoxide is present during the reductive amination, The molar ratio of carbon monoxide to hydrogen is less than about 0.15: 1, preferably less than about 0.1: 1. Optimally less than about 0.05: 1. The polyamine produced by the present invention can be easily recovered, and can be used as a rubber chemical, urethane / Urea materials, coatings, adhesives, Suitable for sealants, where the polyamine contains pendant secondary amine groups It is also suitable for the construction of three-dimensional networks via bonds that are not available for tertiary amines. A fourth aspect of the invention is the formula: (In the formula, P₁A repeating unit containing P and P₂Repeating units containing Representing a repeating unit of a polymer containing natively aminated olefinic unsaturation, P_Three Is the reaction of the same polymer containing olefinic unsaturation with reactive carbon-carbon double bonds. R, R'and R "independently represent an aliphatic group, an aromatic group, an alicyclic group, or a unit. Selected from the group consisting of substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups, P₁ A repeating unit containing P and₂The sum of repeating units containing₁A repeating unit containing P and₂Anti-including Return unit and P_ThreeAbout 2 to about 90% of the sum of repeating units, P₂The number of repeating units containing₁ A repeating unit containing P and₂About 5 to about 95% of the number of repeating units containing However, P₁A repeating unit containing P and₂The number of repeating units containing₁A repeating unit containing P and₂Including Mu repeat unit and P_ThreeRepeat units of at least 1% of the total number of repeat units) Containing polyamines. Substituents on the substituted aliphatic, aromatic and alicyclic groups are (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The polyamine produced according to the present invention has the formula: Of the pendant aldehyde group. Essentially all of the aldehyde groups in the realdehyde or poly (tertiary amine) are reductive Converted to amine groups during amination. Furthermore, the polyamines produced according to the invention Is the formula: When containing a pendant secondary amine group of the polyamine has the formula: (In the formula, R'is an aliphatic group, an aromatic group, an alicyclic group, a substituted aliphatic group, a substituted aromatic group or And substituted alicyclic groups and combinations thereof). Essentially free of positions, in other words polyamines from pendant secondary amine groups. It is essentially free of derivatized tertiary amine groups. A fifth aspect of the invention is of the formula: (In the formula, P₁A repeating unit containing P and P₂Repeating units containing Representing a repeating unit of a polymer containing natively aminated olefinic unsaturation, P_Three Is the same poly containing olefinic unsaturation with reactive carbon-carbon double bonds. Represents a repeating unit of a mer, and R, R ', R "and R'" are independently an aliphatic group or an aromatic group. Group consisting of a group, an alicyclic group, a substituted aliphatic group, a substituted aromatic group and a substituted alicyclic group However, -NRR 'is different from -NR "R'", and₁Repeating unit containing And P₂The sum of repeating units containing₁A repeating unit containing P and₂A repeating unit containing P and_ThreeRepetition 2 to about 90% of the sum of units, P₁The number of repeating units containing₁A repeating unit containing P₂About 5 to about 95% of the total number of repeating units including P₁A repeating unit containing P₂The number of repeating units containing₁A repeating unit containing P and₂A repeating unit containing P and_ThreeRepeat unit Of each of which is at least 1%). The substituents on the substituted aliphatic, aromatic and alicyclic groups are as defined above.Hydroformylation According to the invention, the polyamine contains the olefinic unsaturation produced according to the invention. Polymer or poly (tertiary amine) containing a reactive carbon-carbon double bond. It is prepared from an aldehyde-functionalized polymer obtained by rumylation. Polymers containing olefinic unsaturation useful in the method of the present invention include multiple carbon-carbons. C with an elementary double bond_Four-C_TenMonomers (eg butadiene, isoprene, cyclo Pentadiene), cyclopentadiene, 1,3-pentadiene, 1,4-penta Diene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene Formed from dimers such as 1,2,4-hexadiene and 1,3,5-hexatriene Can be a homopolymer. The porphyrins containing olefinic unsaturation used in the present invention. The limer can be of any of its isomeric configurations. For example of polybutadiene In some cases, cis-1,4, trans-1,4 or trans-1,2 configuration or It can be a mixture. Further, the polymers useful in the method of the present invention are carbon-carbon double Two or more monomers each capable of forming a polymer segment containing a bond It may be a copolymer formed from a compound, such as polybutadiene segment Copolymers, such as poly (butadiene-isoprene), poly (butadiene) It is a copolymer such as tadiene-1,4-pentadiene). Polymers containing olefinic unsaturation useful in the method of the present invention include olefins. Polymer segment Polymer containing at least one monomer as described above, which is capable of At least one copolymerizable vinyl monomer that does not form a segment [eg Crylamide, acrylonitrile, styrene, acrylate, alkyl vinyl ether Ether, alkyl vinyl ketone, etc. and mixtures thereof and C of such monomers.₁ -C₂₀Hydrocarbyl derivatives (eg α-methylstyrene, methyl acrylate) Etc.)]. As is well known, such materials are It is conventionally formed by the dical, cationic or anionic polymerization method. These ports Limers are poly (butadiene-acrylonitrile), poly (butadiene-styrene) ), Acrylonitrile-butadiene-styrene (ABS) resin, ethylene-propylene A wide variety of products such as ropylene-diene (EPDM) polymers can be easily commercialized Available at. Polymers containing olefinic unsaturation will be Sufficient carbon to function as the active precursor of the desired polyaldehyde product -An olefin-free monomer to any desired extent, so long as it contains carbon double bonds. Group can be used. Polymers containing olefinic unsaturation useful in the method of the present invention Is a polymer material containing residual carbon-carbon double bonds due to branching, isomerization, etc. The olefinic monomer produced (eg ethylene, propylene, 1-butene, 1 -Pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pen Ten, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 2,4,4 -Trimethyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-bu It can also be formed of ten. Suitable polymers containing olefinic unsaturation include polyethylene, polypropylene. Homopolymers such as pyrene, polybutene, polybutadiene and polyoctene; poly (Ethylene propylene), Poly (ethylene octene), Poly (ethylene isobutyrate) Len), poly (ethylene-1-butene), poly (ethylenehexene) and poly ( Copolymers of olefins such as propylene octene); Copolymers of two copolymerizable mono-olefin monomers, eg two or more olefins Copolymers of ethylene and diene monomers, specifically poly (ethylene propylene diene Monomer) (EPDM), poly (ethylene vinyl acetate), poly (ethylene Vinyl alcohol), poly (ethylene ethyl acrylate) Rate), poly (propylene methyl acrylate), dienes and acrylonitrile , Such as copolymers of butadiene and acrylonitrile. It is. Satisfactory diene monomers include 1,4-hexadiene, 2-methyl-2,4 -Pentadiene, 1,4,9-decatriene and 11-ethyl-1,11-tri Linear (acyclic) dienes such as decadienes; monocyclic such as 1,5-cyclooctadiene Diene; 5-ethylidene norbornene (ENB), 5-methylene-2-norbol Nene, 5-isopropylidene-2-norbornene and 2-methyl-bicyclo- ( 2.2.1) -2,5-Heptadiene and other dienes; bicyclo- (4.3.0)- 3,7-Nonadiene, 5-methyl-bicyclo- (4.3.0) -3,7-nonadiene Ene, 5,6-dimethyl-bicyclo- (4.3.0) -3,7-nonadiene and Fused ring bicyclic dienes such as bicyclo- (3.2.0) -2,6-heptadiene; 4 -Vinylcyclohexene, 1,2-divinylcyclobutane and 1,2,4-tri Alkenyl-substituted monocyclic dienes such as vinylcyclohexane; and dicyclopentadiene Examples include tricyclic dienes such as ene (DCPD). For use in the practice of the invention Suitable EPDM rubber gray Are commercially available. Rubber World Blue Book 197 5 Ed. , Materials and Compounding Ingr editors for Rubber, pp 406-410. Suitable EPDM Rubber is manufactured by Universal Chemical Company, Inc. , Mi marketed under the tradename Trilene® by ddlebury, CT , For example Trilene® 66 and 67 (ENB diene monomer) , Trilene® 55 and 65 (DCPD diene monomer) is there. Other suitable EPDM rubbers include the diene monomer 5-isopropylidene. Examples include 2-norbornene. Although not particularly necessary, The ratio of ethylene to propylene in EPDM rubber is about 40/60 to about 50/50. Is preferred. The preferred polymers containing olefinic unsaturation useful in the present invention are polybutadiene and polybutadiene. It is poly (ethylene propylene diene monomer). A polymer or polymer containing olefinic unsaturation to undergo a hydroformylation reaction Contains a reactive carbon-carbon double bond The poly (tertiary amine) must contain some unsaturation, ie syngas ( Carbon-carbon, which is the site where carbon monoxide and hydrogen) form an aldehyde (-CHO) group. It must contain a double bond. This unsaturation is due to the polymer backbone and / or Can be present on the pendant (eg in the case of EPDM polymers). Preferably The degree of unsaturation in a polymer containing reffinic unsaturation is equivalent to one polymer chain (or molecule) 1 carbon-carbon double bond to about 1 carbon-carbon double bond per 4 carbon atoms The range is up to. Methods for measuring polymer unsaturation are well known. For example, tired The degree of harmony can be measured by ASTM D-1638-59T. Infrared spectroscopy Law or¹The degree of unsaturation can also be measured using 1 H NMR. This method is Wi Llard et al., Instrumental Methods of Analysis. sis, Chapters 5 and 6, Van Nostrand Co. , Inc. , Pub It may be carried out by a well-known method as described in Lichers (1965). Can be. Alternatively, well known titration methods can be used. The preferred method for measuring unsaturation is¹ 1 H NMR. Suitable polymers containing olefinic unsaturation range from about 300 to About 250,000, preferably about 600 to about 150,000, optimally about 100 0 to about 15,000 weight average molecular weight (M_w) Is a polymer having. Polymers containing olefinic unsaturation or poly containing reactive carbon-carbon double bonds (Tertiary amine) as a molten phase or dissolved in an inert solvent to form carbon monoxide and hydrogen Mix. Glass transition temperature corresponding to a specific polymer when no solvent is used (T_g) After heating the polymer to a higher temperature, add carbon monoxide and hydrogen and mix I do. When using an inert solvent, dissolve the polymer in the solvent and then use carbon monoxide. Add hydrogen and hydrogen and mix. A suitable inert solvent to dissolve the polymer is Mention may be made of ruene and toluene / dimethylformamide mixtures. Hydrogen and carbon monoxide have a molar ratio of hydrogen to carbon monoxide of about 1: 3 to about 3: 1, preferably. Preferably, it is mixed with the polymer in a ratio of about 1: 2 to about 2: 1, optimally about 1: 1. You. It is preferable to maintain essentially an initial molar ratio of hydrogen to carbon monoxide during all steps of the reaction. Good. After the addition of carbon monoxide and hydrogen, a suitable catalyst is added to the mixture. Or with hydrogen Before adding carbon monoxide, It may be brought into contact with the mer. Hydroformyl polymer containing olefinic unsaturation A non-limiting example of a suitable catalyst to convert is a Group VIII metal catalyst. Suitable Group VIII metal Is rhodium (I). Examples of suitable rhodium (I) catalysts include dicarboni Leacetylacetonato rhodium (I) (Rh (CO)₂AcAc), cyclo Kutadi entry fluoroacetyl rhodium (I) dimer ([Rh (COD) ( O₂CCF_Three)]₂), RhH (CO) (PPh_Three)_ThreeAnd the like. Preferred hydro Formylation catalyst is Rh (CO)₂AcAc and RhH (CO) (PPh_Three)_ThreeIs . The hydroformylation reaction is carried out under a carbon monoxide / hydrogen atmosphere. Hydroform The carbon monoxide / hydrogen pressure during the milling reaction is from about 50 psig to about 1000 psig. , Preferably from about 200 psig to about 1000 psig. Hydroformylation The temperature of the reaction is about 25 ° C to about 200 ° C, preferably about 50 ° C to about 150 ° C, optimally Is about 80 ° C to about 120 ° C. Pendane produced during the hydroformylation reaction. The functional group density of polyaldehyde or poly (tertiary amine) containing a toaldehyde group is Starting polymers containing olefinic unsaturation or polymers containing reactive carbon-carbon double bonds. Li (tertiary amine) Depends on the amount of carbon monoxide and hydrogen associated with the degree of unsaturation present. Polyal The functional group density of the dehydrate depends on the carbon monoxide / hydrogen gas uptake during the hydroformylation reaction. It is controlled by measuring. Thus polymers containing olefinic unsaturation or Is an aldehyde located on a poly (tertiary amine) containing a reactive carbon-carbon double bond Can be measured and controlled. Stop the reaction when the desired functional group density is reached it can. Hydroformylation catalysts, especially rhodium (I) catalysts, are converted to metal rhodium and Polymer containing reffinic unsaturation 10⁶Hydro at a ratio of less than about 200 parts per part Used in the formylation reaction. Therefore, the hydroformylation reaction is economically feasible. That is, the catalyst cost is low and the catalyst can be carried out under relatively mild conditions. The method of the present invention employs a method for hydrating aldehyde groups in polymers containing olefinic unsaturation. Expressing functional group density as mol% of carbon-carbon double bond to be loformylated And control the functional group density of the polyaldehyde in the range of 2 mol% to about 90 mol%. Can be The method of the present invention controls the functional group density of the polyaldehyde within the above range. Can be controlled to any value, but A functional group density in the range of 10 mol% to about 85 mol% is preferred. Similarly, anti Hydroformylation of poly (tertiary amine) containing responsive carbon-carbon double bond According to the method of the present invention, the total functional group density of the poly (tertiary amine) is from 2 mol% to about 90%. Available reactive carbon-carbon double in poly (tertiary amine) such that The functional group density of the aldehyde groups produced by hydroformylating the bond Can be controlled. Total functional group density is a polymer containing olefinic unsaturation Hydroformylation of aldehyde groups before and after reductive amination to tertiary amine groups Mol% of the carbon-carbon double bond that is generated. In one aspect, the polyaldehyde can be recovered prior to reductive amination. Poly When recovering the aldehyde, it can be recovered by any conventional recovery method. For example, when carrying out the hydroformylation reaction in the presence of a solvent (for example, toluene), Reduce the amount of solvent in the reaction mixture and slowly add methanol while stirring the mixture. And the polyaldehyde is precipitated. The polymer is then recovered and reconstituted in the original solvent. Dissolve and reprecipitate with methanol. In this way, the purified polyaldehyde is recovered. be able to.Reductive amination Reductive amination is carried out in a suitable solvent in the presence of a ruthenium-containing imine hydrogenation catalyst. Reacting the polyaldehyde with a primary secondary amine and hydrogen at Reacting the polyaldehyde with a primary and secondary amine in the presence of a polymetal borohydride. It is carried out by Poly (tertiary amine) produced by the method of the present invention Has a ratio of tertiary amine groups to reactive carbon-carbon double bonds in aldehydes in polyaldehydes. It is substantially equal to the ratio of hydrido groups to reactive carbon-carbon double bonds. Poly (3rd order) containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. Amine) reductive amination is suitable in the presence of ruthenium-containing imine hydrogenation catalysts Reacting the poly (tertiary amine) with primary amine or secondary secondary amine and hydrogen in a simple solvent. Or poly (tertiary amine) as described above in the presence of an alkali metal borohydride. Is carried out by reacting with a primary amine or a secondary secondary amine, provided that reduction Amination was carried out with primary amines in the presence of alkali metal borohydrides. Primary amine is a sterically hindered aliphatic or cycloaliphatic primary amine or aromatic It is a primary amine. The polyamine produced by the method of the present invention is a secondary amine. Group or a tertiary amine group derived from a secondary secondary amine and a reactive carbon-carbon double bond Polyethers containing controlled amounts of aldehyde groups and reactive carbon-carbon double bonds Substantially equal to the ratio of the aldehyde group in the (tertiary amine) to the reactive carbon-carbon double bond. New The functional group density of the polyamine and / or poly (tertiary amine) depends on the polyaldehyde and And / or the functional group density of the aldehyde groups in the poly (tertiary amine). Therefore , The functional group density of the polyamine is the total pendant amine functional group density Carbon in Polymers Containing Olefinic Unsaturation Used to Make Dehydrates- Easy to range from 2 mol% to about 90 mol% based on the level of carbon double bonds Can be controlled. Therefore, the total pendant amine functional groups in the polyamine The density depends on the specific functional group density desired for the end use of the polyamine, from 2 mol% to Is any value in the range of about 90 mol%, preferably about 10 mol% to about 85 mol%. obtain. Pendant tertiary amine groups derived from primary and secondary amines in polyamines Has a functional group density of about 5 to about 95% of the total pendant amine functional groups, provided that the first Functional density of pendant tertiary amine groups derived from secondary amines of Is at least 1 mol% and is a pendant secondary amine group or a secondary secondary amine. The functional group density of pendant tertiary amine groups derived from is at least 1 mol% . Therefore, the balance of the total pendant amine functional groups is the pendant secondary amine in the polyamine. Functional groups of amine groups or pendant tertiary amine groups derived from secondary secondary amines Derived from density. Suitable for use in the process of the invention using a ruthenium-containing imine hydrogenation catalyst The amine has the formula RR'NH (wherein R and R'are independently aliphatic, aromatic, Selected from the group consisting of cyclic groups, substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups. Secondary amine represented by the formula₂(In the formula, R has the same meaning as above. Is a primary amine. First secondary amine and second secondary amine In an embodiment of the present invention in which a primary secondary amine is a secondary secondary amine, R and R'are Chosen to be different than Min. In the case of substituted aliphatic, substituted aromatic and substituted alicyclic groups In this case, the substituents on the aliphatic, alicyclic or aromatic groups are (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. Of the present invention When a substituted primary or secondary amine is used in the process, the preferred substituents are -OR.₁as well as -NR₁R₂And the optimal substituent is R₁And R₂One side Hydrogen and R₁And R₂The other is an aliphatic or alicyclic group, -NR₁R₂Is . The term “aromatic” as used herein includes one or more rings and is preferably Means an unsaturated cyclic hydrocarbon containing from 6 to about 14 carbon atoms. Non-aromatic ring Non-limiting examples include phenyl, naphthyl and the like. As used herein The term "aliphatic" means a straight or branched chain hydrocarbon containing from 1 to about 22 carbon atoms. To taste. The term "cycloaliphatic" as used herein refers to a cycloaliphatic compound, i.e. a closed ring structure. Including carbon atom arrangement during production, having 3 to about 18 carbon atoms, preferably Means 3 to about 8 hydrocarbon compounds. A non-limiting example of an alicyclic ring is sikh Examples include lopropyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. . Non-limiting examples of suitable primary amines include methylamine, ethylamine, ether Sopropylamine, n-butylamine, n-hexylamine, n-octylamine Amine, 2-aminoheptane, cyclohexylamine, cyclooctylamine, ani Phosphorus, benzylamine, 2-aminoethanol, 4-amino-1-butanol, 2-amino-1-butanol, 6-amino-1-hexanol, 2-amino-1 -Methoxypropane, 4-aminophenol, 4-aminocyclohexanol, 4-aminobenzotrifluoride, N-isopropyl-4-aminophenylami N, N- (2-butyl) -4-aminophenylamine, N-methylisoamyl- 4-aminophenylamine, N-cyclohexyl-4-aminophenylamine, N-octyl-4-aminophenylamine, 4-aminodiphenylamine, N, N-dimethyl ethylene diamine etc. are mentioned. Non-limiting examples of suitable secondary amines include dimethylamine, diethylamine, Methyl ethylamine, n-methyl ether Tanolamine, di (n-propyl) amine, di (ethylhexyl) amine, Peridine, morpholine, piperazine, di (n-heptyl) amine, N-methyl Niline, 2-aminooctane, 4-aminodiphenylamine, N-phenyl-N '-Cyclohexyl-p-phenylenediamine, N, N'-bis- (1-methyl Propyl) -p-phenylenediamine, dibenzylamine, methylnaphthylami And the like. Used in the method of the present invention using an alkali metal borohydride. Suitable amines for the reaction are secondary amines, sterically hindered aliphatic or cycloaliphatic primary amines as described above. Amines, primary aromatic amines, and substituted sterically hindered aliphatic or cycloaliphatic and aromatic primary amines 1 amine. Substituted sterically hindered aliphatic or cycloaliphatic and aromatic primary amines The substituents on the aliphatic, alicyclic or aromatic groups are as described above. Non-limiting example of a suitable sterically hindered aliphatic or cycloaliphatic amine is isopropyl Amine, cyclohexylamine, cyclooctylamine, isobutylamine and Cyclopentylamine may be mentioned. In a first aspect of the invention, the amount of primary secondary amine used in the method of the invention is In secondary amine 1 and polyaldehyde Can be conveniently expressed as a molar ratio of -CHO, i.e. the amount of primary secondary amine Depends on the functional group density of the polyaldehyde. Such a molar ratio is about 1: 1 to about 30: 1, preferably about 1: 1 to about 20: 1, optimally about 2: 1 to about 10: 1. possible. The poly (tertiary amine) produced contains pendant tertiary amine functional groups. Almost all of the aldehyde groups are aminated. The first method used in the method of the present invention The amount of the amine or secondary secondary amine is the primary amine and -CHO in the poly (tertiary amine). Can be conveniently expressed as a molar ratio of: primary amine or secondary secondary amine Depends on the functional group density of the aldehyde groups in the poly (tertiary amine). This The molar ratio is about 1: 1 to about 30: 1, preferably about 1: 1 to about 20: 1, optimally Can be from about 2: 1 to about 10: 1. The generated polyamine is the second pendant And tertiary amine functional groups, and almost all of the aldehyde groups are reductively aminated. In a second aspect of the invention, of the primary secondary amine used in the method of the invention The amount is conveniently expressed as a molar ratio of primary and secondary amine to -CHO in the polyaldehyde. That is, the amount of primary and secondary amines is the functional group density of the polyaldehyde. And the desired percentage of pendant aldehyde groups to be reductively aminated. Such a molar ratio depends on the amount of aldehyde groups to be reductively aminated with the primary and secondary amines. It is typically about 1: 1 depending on Alternatively, the molar ratio is in polyaldehyde Can be 0.01: 1 to 0.99: 1 depending on the total amount of aldehyde groups of Book The amount of primary amine or secondary secondary amine used in the method of the invention may vary from the primary amine or the secondary amine. Is a molar ratio of the secondary secondary amine to —CHO in the poly (tertiary amine) for convenience. Can be represented, that is, the amount of primary amine or secondary secondary amine is poly (tertiary amine It depends on the functional group density of the aldehyde group in (). Such a molar ratio is about 1: 1 to About 30: 1, preferably about 1: 1 to about 20: 1, optimally about 2: 1 to about 10: 1. Can be. The polyamine produced contains pendant amine functional groups and Almost all of the do groups are reductively aminated. In the third aspect of the present invention, the amount of total amine used in the method of the present invention is It can be conveniently expressed as a molar ratio of total amine and -CHO in polyaldehyde. That is, the amount of total amine depends on the functional group density of the polyaldehyde. like this The molar ratio is about 1: 1 to about 30: 1, preferably about 1 : 1 to about 20: 1, optimally about 2: 1 to about 10: 1. In the method of the present invention The amount of secondary amine and primary amine used depends on the molar ratio of primary amine to secondary amine. Can be conveniently expressed as Such molar ratio is (1) polyamine product Desired amount of pendant secondary and tertiary amine groups and (2) primary and secondary amine phases above It depends on the reactivity. One of ordinary skill in the art will appreciate that a limited number of daily The desired molar ratio of primary amine to secondary amine can be readily determined by experimental U. The polyamine produced contains pendant tertiary and secondary amine functional groups and is Almost all of the dehydrate groups are reductively aminated. The catalyst used in the reductive amination reaction is a carbon-carbon double bond during the reductive amination. A ruthenium-containing imine hydrogenation catalyst that does not hydrogenate bonds. Ruthenium-containing a Min hydrogenation catalysts can take a wide variety of forms. For example ruthenium (IV) oxide hydration Acid, such as anhydrous ruthenium (IV) dioxide and ruthenium tetroxide (VIII) Ruthenium can be added to the reaction mixture in the form of the halide. Alternatively, lute chloride Ruthenium (III) bromide, Ruthenium (III) bromide, Ruthenium (III) iodide, Ruthenium (III) tricarbonyl iodide, It is added as a salt of an inorganic acid such as anhydrous ruthenium (III) chloride and ruthenium nitrate. Or ruthenium (III) acetate, ruthenium (III) naphthenate, It may be added as a salt of a suitable organic carboxylic acid such as ruthenium valerate. , Ruthenium (III) acetylacetonate (ruthenium (III) ac rutheni containing a carbonyl-containing ligand, such as etylacetonate) It may be added as an um complex. In addition, carbonyl or ruthenium carbonyl hydride Ruthenium may be added to the reaction zone as a ru derivative. In this case, with a good example And triruthenium dodecacarbonyl and other ruthenium carbonyl hydride [ For example H₂Ru_Four(CO)₁₃And H_FourRu_Four(CO)₁₂] And substituted carbonyl species (eg For example, tricarbonyl ruthenium (II) chloride dimer [Ru (CO)_ThreeCl₂]₂) Is mentioned. Suitable ruthenium-containing imine hydrogenation catalysts include ruthenium oxides and organic catalysts. Ruthenic acid ruthenium salt, and ruthenium carbonyl or ruthenium hydride Bonyl derivatives are mentioned. Of these, ruthenium (IV) dioxide hydrate and tetraacid Ruthenium oxide, anhydrous ruthenium (IV) oxide, acetic acid Ruthenium, ruthenium (III) acetylacetonate and triruthenium dodecane Cacarbonyl is particularly preferred. The optimal ruthenium-containing imine hydrogenation catalyst is tri Ruthenium Dodecacarbonyl (Ru_Three(CO)₁₂). When a ruthenium-containing imine hydrogenation catalyst is used, the reductive amination is hydrogen. It is carried out in an atmosphere. Reductive amination may optionally change the ratio of carbon monoxide to hydrogen. Less than about 0.15: 1, preferably less than about 0.1: 1, optimally about 0.05: 1 It can be carried out under full hydrogen and carbon monoxide atmosphere. Hydrogen during reductive amination Or hydrogen / carbon monoxide pressure from about 150 psig to about 1000 psig, preferably Or about 200 psig to about 1000 psig. The temperature of reductive amination is about 110 ° C to about 200 ° C, preferably about 120 ° C to about 150 ° C. The alkali metal borohydride used in the reductive amination is preferably borohydride. Sodium or lithium, optimally sodium borohydride. Suitable al A non-limiting example of a potassium metal borohydride is NaBH (O₂CCH_Three)_Three, N aBH_ThreeCN, NaBH_Four, LiBH_FourAnd mixtures thereof. one Generally suitable alkali metal borohydrate Oxides have good potency and good results, so NaBH (O₂CCH_Three)_ThreeOver And NaBH_ThreeIt is CN. Reductive amination is typically carried out in the presence of a suitable solvent system. Suitable solvent Non-limiting examples of systems include toluene, xylene, dimethylformamide (DMF ) And a mixture of alkanes or cycloalkanes (eg DMF / cyclohexane), Ethers (eg tetrahydrofuran), chlorinated hydrocarbons (eg dichloroethane) Tan) and the like, and mixtures thereof. Using ruthenium-containing imine hydrogenation catalyst A generally preferred solvent system for use is a mixture of DMF and cyclohexane. A A generally preferred solvent system when using Lucari metal borohydride is tetrahydrofuran. It is orchid. The polyamine produced by the method of the present invention may be recovered by any conventional recovery method. Can be Examples of such recovery methods are described in the examples below. Example Example 1 This example illustrates the preparation of polybutadiene-based polyaldehydes. Polybutadiene (Revertex N4500; 45% vinyl MN = 45) A sample of 1000.19 g of 00) was dissolved in 1300 mL of toluene. N₂Mood The polymer solution was poured into a 1-gallon autoclave under atmospheric pressure. Then trif 6.9 g of phenylphosphine and hydridocarbonyltris (triphenylphosphine) N) 0.42 g of rhodium (I)₂Added to autoclave under atmosphere. Oh Close the toclave and place the autoclave at 200 psi N₂After pressurizing with N₂Moth N by exhausting the vent₂I deaerated further. Then autoclave 400 psi N₂Heated down to 80 ° C. N₂In the autoclave after removing 160 psi 1: 1 CO / H at 80 ° C₂Was charged. 24 from graduated container 87 psig 1: 1 CO / H₂The reaction mixture to 1000 rpm until And stirred. After evacuating the autoclave, the polymer product was taken out. Haute The reeve was washed with 100 mL of toluene and the wash was added to the polymer product. Generate The product solution was concentrated by rotary evaporation. This polymer solution is then It was slowly added dropwise to a solution containing 4: 1 methanol / water. The solution is separated into two phases And decanted the upper phase. Bottom The polymer phase was dissolved in toluene and the above precipitation procedure was repeated. From this procedure The limer product was isolated. Infrared spectra of thin films of polymer products on KBr plates 1730 cm^-1Showed aldehyde absorption in.¹H NMR is P (Bd) 32.67% of the double bonds in the polymer were hydroformylated. Indicated. The aldehyde protons are linked to the olefinic peak in the polymer backbone. Percentage of integrated and hydroformylated butadiene units Is calculated. Selective¹1 H NMR resonance: δ 9.75 major (> 90%); 55 and 9.65 minor, aldehyde; 4.8-5.1, m, CH ₂ = C, 5.15-5.65, m. Example 2 This example is a poly (tertiary amine) using the polyaldehyde prepared in Example 1. The production of is illustrated. The toluene solution of polyaldehyde (1) produced in Example 1 was concentrated under reduced pressure. Next 306 g of product 1 in 909 mL of DMF, 573 mL of cyclohexane, 318 g of methylamine and 3.1 g of ruthenium carbonyl were added to a 1-gallon autoclave. I put it in the rave. Close the autoclave, and 0 psig CO / H₂Purged with. 100 psig CO in the autoclave / H₂And H of 900 psig₂1 while stirring at a speed of 1000 rpm Heated to 20 ° C. Gas uptake began when the reaction temperature reached about 100 ° C. Moth The reaction was allowed to proceed until the uptake stopped (about 4 hours). After cooling to room temperature, auto The contents of the clave were removed and placed in three 2 L separatory funnels for phase separation. Leakage The total volume level was recorded on each of the doves. Remove the lower reddish brown DMF layer It was thrown out and discarded. Add 300 mL of DMF to each separatory funnel, and add cyclohexane. The liquid level in the flask was then increased to the original volume. Shake the funnel, cyclo The hexane layer was extracted with DMF and the separation procedure was repeated. Total 3 DMF extraction procedures I went there. Cyclohexane layer with medium porosity glass-Frit Buchner funnel ( glass-fritted buchner funnel), and Add ene and rotovaped at 50 ° C. to remove residual DMF. I left. The polymer was dried in a vacuum line for 2 hours. d_Four -In acetic acid¹1 H NMR shows complete conversion of the aldehyde to a tertiary amine group did. Then darken the aminated polymer Stored in toluene in place. Selected proton NMR resonance (selected pr) oton NMR resonances (CD_ThreeCO₂D): Olefinic pi Ark: δ 5.45-5.1, m, and 4.9-4.65, m, CH ₂ = C; δ2 . 65, s, (CH ₃ )₂NH +; δ2.9, s, Polymer-CH ₂ NH (CH_Three)₂ . No aldehyde peak was detected. Example 3 In this example, the poly (aldehyde) prepared by the method of Example 1 was used. 3 amine). 33 in hydroformylated polybutadiene prepared by the method of Example 1 % Poly-aldehyde having carbon-carbon double bond (63.14 g) was dried with 4Å molecular sieve. Dissolve in 100 mL of dry toluene and 20 mL of methanol, and use a thermometer, addition funnel and magnet. This solution was placed in a 2 L 3-neck round bottom flask equipped with a stir bar. The solution is further TH It was diluted with 500 mL of F and 40 mL of methanol. N₂After cooling down to 5 ℃, Methylamine (50 g) was added with stirring. After 15 minutes 4. in dioxane solution. 85.8 mL of 5M HCl was added slowly to the solution via an addition funnel. Finally Cyanoborohydride Add 17 g of sodium slowly with a funnel and rinse the flask with 20 mL of THF. Was. The solution was stirred for 40 hours and allowed to warm slowly to room temperature. For polymer solution After adding 60 mL of water and stirring for 1 hour, it was filtered. Concentrate the filtrate to a volume of 200 mL. After shrinking and allowing to stand for 2 hours, the upper polymer phase was added with 400 mL of methanol and 100 m of water. It was slowly added dropwise to the mixture of L. The bottom polymer phase was decanted and separated. Sinking The procedure was repeated. 64.6 g of poly (tertiary amine) was isolated. Elemental analysis ( Found:% C80.62,% H11.66,% N6.62. d_Four-In acetic acid¹H NMR showed that the aldehyde was completely converted to tertiary amine groups. Choice Pro Ton NMR resonance (CD_ThreeCO₂D): Olefinic peak: δ 5.45-5.1 m, and 4.9-4.65, m, CH ₂ = C; δ2.65, s, (CH ₃ )₂NH +; Δ2.9, s, polymer-CH ₂ NH (CH_Three)₂. Aldehyde peak detected Was not done. Example 4 This example is based on a polybutadiene with a controlled amount of aldehyde groups. 1 illustrates the production of poly (tertiary amine). Carbon-carbon double bond 3 prepared in Example 2 and functionalized with a dimethylamino group Poly (tertiary amine) based on polybutadiene containing 2.67% (30 g) Was dissolved in 180 mL of toluene in a 300 mL Parr reactor. HRh (CO ) (PPh_Three)_Three(0.009g) and PPh_Three(0.09g) was added to the reactor . The reactor was sealed and then purged with 25 psig nitrogen three times. 3 ps reactor Heated to 100 ° C. under ig nitrogen. React when the reactor temperature stabilizes at 100 ° C 600 psig syngas (H₂/ CO 1: 1). Scale Monitor gas uptake and cool reactor when desired amount of gas is uptaken Then, it was evacuated and the reaction was completed. The reaction mixture was then removed from the reactor. Small sun Dry the pull under reduced pressure,¹It was analyzed by 1 H NMR. According to NMR, the starting poly ( 43.07% of the double bonds in the tertiary amine) or 29.00% of the first double bonds It was found to be functionalized with aldehyde groups. Example 5 This example demonstrates that poly (3rd order) containing a controlled amount of aldehyde groups prepared in Example 4 was used. Amine) polybutadiene The production of polyamines based on A poly (tertiary amine) containing a controlled amount of aldehyde groups prepared in Example 3 Concentration on a rotary evaporator removed almost all of the toluene present. Next, the polymer was mixed with 60 mL of dimethylformamide (DMF) and 60 mL of cyclohexane. Dissolved in mL mixture. Ru_Three(CO)₁₂(0.100g) was added and Pyramine (3 eq / CHO; 0.318 mol; 18.80 g) was added. reaction Seal the vessel, H₂Purged 6 times with / CO (1: 1). H in the reactor₂/ CO (1: 1) to 67 psig and then H to total pressure of 412 psig₂Was charged. The reactor was heated to 120 ° C. When the temperature of the reactor stabilizes, 600 ps is added to the reactor. H up to ig₂Was charged and allowed to react overnight. The reactor was cooled and evacuated. Reaction mixture The product was filtered through glass wool and placed in a 250 mL separatory funnel, and the phases were separated. Shi After washing the hexane layer with DMF (60 mL) three times, the cyclohexane layer was separated. , All solvent was removed. The polymer was then redissolved in toluene. Vacuum dry the sample It was dried and analyzed. d_Four-In acetic acid¹1 H NMR shows dimethylamido bound to a polymer. And characteristic peaks of isopropylamino group were shown. N Unreacted aldehyde was not detected by MR. Elemental analysis: Calculated value: C78.0 2%, H12.84%, N9.14%; Found: C77.79%, H12.98. %, N 9.04%. The above results indicate that the polymer has secondary and tertiary amine groups as desired. It shows that it was selectively functionalized. The final product was a stable soluble polymer . Example 6 This example shows a controlled amount when the secondary amine group is added before the tertiary amine group. Of stable soluble polyamines containing secondary and tertiary amine groups of It is a comparative example to prove.Polyaldehyde: Polybutadiene (25.0 g, Aldrich 20,050-6; 4500 M. N. 45% vinyl; 55% cis and trans) in 300 mL Parr solution I put it in the reactor. Triphenylphosphine (PPh_Three0.30 g) into the reactor In addition, HRh (CO) (PPh_Three)_Three(0.03g) was also added to the reactor. reaction The body was dissolved in 150 mL of toluene and the reactor was closed. 25 while stirring the reactor Reactor under 2 psig nitrogen after purging with psig nitrogen Was heated to 100 ° C. Once the reactor temperature has stabilized, add 200 psig to the reactor. H₂/ CO (synthesis gas) was charged. To observe the pressure drop in a graduated container More gas uptake was monitored. Once the proper amount of gas is ingested, the reaction mixture is rapidly The reaction was stopped by cooling and venting the synthesis gas. Then the reaction mixture is charged with nitrogen. Purge (3 x 25 psig) and remove from reactor. Rotary solution It was concentrated by evaporation. Toluene the polymer with methanol / water (4: 1) The precipitate separated from the solution. Decant solvent, redissolve polymer in toluene, Precipitated with methanol / water (4: 1). Redissolve the polymer in toluene and Dry pull¹ 1 H NMR analysis was performed.¹1 H NMR is based on aldehyde groups 33 . It showed 85% functionalization.Poly secondary amine: Aliquot of polyaldehyde solution (12.69 g solution; 5.0 g polymer) Fractionation was performed and toluene was removed by rotary evaporation. Polymer Dissolve in methylformamide (DMF), and add DMF to a total volume of 75 mL. Transferred to a 00 mL Parr reactor. Ruthenium carbonyl (Ru_Three(CO)₁₂ 0.01 g) and isopro Pyramine (3.0 eq; 6.74 g) was added to the reactor. Cyclohexane (7 5 mL) was added to the reactor and the reactor was closed. Reactor to 60 psig syngas ( H₂Purged twice with / CO; 1: 1). Charge reactor with 60 psig syngas After filling, hydrogen was filled up to a total pressure of 400 psig. Reactor with inlet valve closed Was heated to 120 ° C. When the reaction was allowed to proceed for 7 hours, gas uptake was stopped at this point. It was stopped. After the reactor was cooled and evacuated, it was purged with 25 psig nitrogen three times. Was. The reaction mixture was removed from the reactor and the phases were separated in a 500 mL separatory funnel. When the phase separation was complete, the lower DMF layer was removed. DMF (75 mL) and cyclohex Add Sun (30 mL) to the polymer solution, mix, and then phase separate to cyclohexane. A second extraction of layers was performed. The DMF layer was removed and the cyclohexane layer was -Dried with an evaporator. The polymer was redissolved in toluene. Polymer Of recoat¹1 H NMR shows that the aldehyde group becomes an isopropylamine group on the polymer. It was shown that it was converted.Poly secondary amine-aldehyde: Dissolve isopropylamino-substituted polybutadiene in toluene and add 100 mL of P The arr reactor was charged. Trife Nylphosphine (1.5 g) and HRh (CO) (PPh_Three)_ThreeAnti (0.03g) In addition to the reactor, it was washed with a small amount of toluene (~ 5 mL). Close reactor, 25 ps Purged with ig nitrogen 3 times. Then place the reactor under 2 psig nitrogen to 100 ° C. Heated. Once the reactor temperature equilibrated, 200 psig of syngas was charged. Eye The reaction was allowed to proceed until 55 psig of gas had been taken up from the vessel. Reactor Was cooled and evacuated, then purged with 25 psig nitrogen three times. Reaction mixture It was taken out of the reactor, put in a bottle, sparged with nitrogen, and then stored in a freezer. Dissolution Dry an aliquot of the liquid in a vacuum line,¹1 H NMR analysis was performed. Active on polymer Due to the presence of the formyl group and the secondary amine group, an aliquot can be used for a very short time (30 seconds ) Dried to remove most of the toluene. A long time dried aliquot gels , Not soluble in organic solvent. Then the polymer is added to CDCl_ThreeMelted into. Of polymer¹ 1 H NMR showed that 17.42% of the first double bond in the polymer was hydroformylated. It was shown that it was done.Reductive amination of poly secondary amine-aldehydes Poly secondary amine-aldehyde was dissolved in toluene and 300 mL Parr reaction was performed. I put it in a bowl. Ruthenium carbonyl (Ru_Three(CO)₁₂0.100 g) was added to the reactor. Another weight that weighs itself Add 50 mL of DMF to the rusco and stopper with a rubber stopper. Dimethylamine was bubbled in until it was dissolved in DMF. Dimethyl The amine solution was added to the reactor and the reactor was closed. Set the reactor to 100 psig of synthetic gas. Su (1: 1 H₂/ CO) twice and then fill with synthesis gas up to 60 psig. I filled it. Then fill the reactor with hydrogen to a total pressure of 400 psig and then turn on the inlet valve. The reactor was closed and heated to 120 ° C. The reaction was allowed to proceed for 17 hours, at this point The gas intake was stopped at. 25 psig nitrogen after cooling and venting the reactor Purged three times. The reaction mixture was removed from the reactor. Rotary toluene Upon removal from the solution by evaporation, the polymer at this point gelled, It no longer dissolves in organic solvents. This method includes both secondary and tertiary amine groups No stable soluble polymer was produced.

【手続補正書】特許法第１８４条の８【提出日】１９９６年１月４日【補正内容】米国特許第４，６５７，９８４号は触媒としてルテニウム又はロジウムホスフィンを使用して一酸化炭素、水素、高分子オレフィン及び第２アミンから高分子ポリ（第３アミン）を製造する方法を開示している。この特許は、これらの特定触媒を使用すると反応が助長され、ひいては内部及びビニルオレフィン基の官能化が助長されると述べている。欧州特許出願第０，６０３，１４６号は官能基密度制御ポリ（第２アミン）及びその製造方法に関している。第２アミンは、オレフィン性不飽和を含むポリマーの触媒を用いたヒドロホルミル化及びそれに続く還元的アミノ化によって製造される。このように、高分子第２及び第３ポリアミンの製造に関する従来技術は、種々の条件下で種々の触媒を使用してビニルオレフィンと内部オレフィンを反応させ得るアミノメチル化反応を教示している。しかしながら、アミノメチル化従来技術はポリアルデヒド又はポリアルデヒドから製造されるポリアミンの官能化度即ち官能基密度、特に種々のアミンペンダント基の量の制御方法について何ら教示していないので、これらの反応はヒドロホルミル化及び還元的アミノ化の反応シーケンスとは著しく異なる。より温和な反応条件を使用して、その結果、制御された量のペンダント第３アミン及びペンダント第２アミン基、又は制御された量の２種の異なるペンダント第３アミン基を含む官能基密度の高いポリマーを生じ、有機溶剤に可溶性のポリマーを生成する、残留反応性炭素−炭素二重結合を含む官能基密度制御ポリアミンの製造方法が実現されるならば極めて望ましいことである。本発明によると、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法が提供され、該方法は、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物（ａｌｋａｌｉｍｅｔａｌｂｏｒｏｈｙｄｒｉｄｅ）の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを第１の第２アミンと接触させて、第３アミン基と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリ（第３アミン）を生成する段階と、ヒドロホルミル化触媒の存在下にヒドロホルミル化条件下で反応性炭素−炭素二重結合を含むポリ（第３アミン）を一酸化炭素及び水素と接触させて、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を第１アミン又は第２の第２アミンと反応させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリアミンを生成する段階とを含み、但し制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ(第３アミン) の還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。１態様において、還元的アミノ化は一酸化炭素の存在下で実施される。別の態様において、ポリアルデヒドは、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。更に別の態様において、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒド又はポリ（第３アミン）中のアルデヒド基の量は、ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される。更に本発明によると、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法が提供され、該方法は、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを、還元的アミノ化すべきペンダントアルデヒド基の百分率に依存する量の第１の第２アミンと接触させて、ポリ（第３アミン）中のペンダント第３アミン基及びペンダントアルデヒド基の和と反応性炭素−炭素二重結合の比がポリアルデド中のペンダントアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しくなるように、制御された量のペンダント第３アミン基、制御された量のペンダントアルデヒド基及び制御された量の反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下でポリ（第３アミン）を第１アミン又は第２の第２アミンと接触させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素− 炭素二重結合の比がポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリアミンを生成する段階とを含み、但し還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。１態様において、還元的アミノ化は一酸化炭素の存在下で実施される。別の態様において、ポリアルデヒドは、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。更に別の態様において、ポリアルデヒドの官能基密度、即ちオレフィン性不飽和を含むポリマー中でアルデヒド基にヒドロホルミル化される炭素−炭素二重結合のモル百分率は、ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される。更に本発明によると、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン基を含むポリアミンの製造方法が提供され、該方法は、（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び炭素−炭素二重結合を含むポリアルデヒド、第１の第２アミン及び第１アミンを接触させて、第３アミン基及び第２アミン基数の和と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリ（第２／第３アミン）を生成する段階を含み、第１の第発明の詳細な説明本発明の第１の態様は、制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法に関し、該方法は、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを第１の第２アミンと接触させて、第３アミン基と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリ（第３アミン）を生成する段階と、（ｂ）ヒドロホルミル化触媒の存在下にヒドロホルミル化条件下で反応性炭素−炭素二重結合を含むポリ（第３アミン）を一酸化炭素及び水素と接触させて、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（ｃ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を第１アミン又は第２の第２アミンと反応させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリアミンを生成する段階とを含み、但し(ｃ)の還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。本発明の第１の態様の方法によると、（ａ）のポリアルデヒドはオレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。また、還元的アミノ化が水素とルテニウム含有イミン水素化触媒の存在下で実施される場合には、（ａ）又は（ｃ）の還元的アミノ化は場合により一酸化炭素の存在下で実施され得る。還元的アミノ化中に一酸化炭素が存在する場合、一酸化炭素と水素のモル比は約０．１５：１未満、好ましくは約０．１：１未満、最適には約０．０５：１未満である。本発明の第２の態様は制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法に関し、該方法は、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを、還元的アミノ化すべきペンダントアルデヒド基の百分率に依存する量の第１の第２アミンと接触させて、ポリ（第３アミン）中のペンダント第３アミン基及びペンダントアルデヒド基の和と反応性炭素−炭素二重結合の比がポリアルデド中のペンダントアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しくなるように、制御された量のペンダント第３アミン基、制御された量のペンダントアルデヒド基及び制御された量の反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（ｂ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で（ａ）のポリ（第３アミン）を第１アミン又は第２の第２アミンと接触させて、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が（ａ）のポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリアミンを生成する段階とを含み、但し（ｂ）の還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。本発明の第２の態様の方法によると、ポリアルデヒドは、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される。また、（ａ）又は（ｂ）の還元的アミノ化が水素とルテニウム含有イミン水素化触媒の存在下で実施される場合には、還元的アミノ化は場合により一酸化炭素の存在下で実施され得る。還元的アミノ化中に一酸化炭素が存在する場合、一酸化炭素と水素のモル比は約０．１５：１未満、好ましくは約０．１：１未満、最適には約０．０５：１未満である。本発明の第３の態様は制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン基を含むポリアミンの製造方法に関し、該方法は、（ａ）（１）水素１態様では還元的アミノ化前にポリアルデヒドを回収することができる。ポリアルデヒドを回収する場合には、任意の慣用回収方法で回収することができる。例えば溶剤（例えばトルエン）の存在下でヒドロホルミル化反応を行う場合には、反応混合物中の溶剤量を減らし、混合物を撹拌しながらメタノールをゆっくりと加えてポリアルデヒドを沈殿させる。次いでポリマーを回収し、元の溶剤に再溶解し、メタノールで再び沈殿させる。こうして精製ポリアルデヒドを回収することができる。還元的アミノ化還元的アミノ化は、ルテニウム含有イミン水素化触媒の存在下に適切な溶剤中で上記ポリアルデヒドを第１の第２アミン及び水素と反応させるか、又はアルカリ金属ホウ水素化物の存在下で上記ポリアルデヒドを第１の第２アミンと反応させることにより実施される。本発明の方法により製造されるポリ（第３アミン）は、第３アミン基と反応性炭素−炭素二重結合の比がポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しい。制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）の還元的アミノ化は、ルテニウム含有イミン水素化触媒の存在下に適切な溶剤中でポリ（第３アミン）を第１アミン又は第２の第２アミン及び水素と反応させるか、又はアルカリ金属ホウ水素化物の存在下で上記ポリ（第３アミン）を第１アミン又は第２の第２アミンと反応させることにより実施され、但し還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである。本発明の方法により製造されるポリアミンは、第２アミン基又は第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しい。ポリアミン及び／又はポリ（第３アミン）の官能基密度は、ポリアルデヒド及び／又はポリ（第３アミン）中のアルデヒド基の官能基密度に依存する。従って、ポリアミンの官能基密度は、合計ペンダントアミン官能基密度が出発ポリアルデヒドを製造するために使用するオレフィン性不飽和を含むポリマー中の炭素− 炭素二重結合のレベルに基づき２モル％〜約９０モル％の範囲となるように容易に制御することができる。従って、ポリアミン中の合計ペンダントアミン官能基密度はポリアミンの最終用途に所望される特定官能基密度に依存して２モル％〜約９０モル％、好ましくは約１０モル％〜約８５モル％の範囲の任意の値であり得る。ポリアミン中の第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度は合計ペンダントアミン官能基の約５〜約９５％であり、但し第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％であり、ペンダント第２アミン基又は第２の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％である。従って、合計ペンダントアミン官能基の残余はポリアミン中のペンダント第２アミン基又は第２の第２アミンから誘導されるペンダント第３アミン基の官能基密度から誘導される。請求の範囲１．制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法であって、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを第１の第２アミンと接触させて、第３アミン基と反応性炭素−炭素二重結合の比が前記ポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリ（第３アミン）を生成する段階と、（ｂ）ヒドロホルミル化触媒の存在下にヒドロホルミル化条件下で反応性炭素− 炭素二重結合を含む前記ポリ（第３アミン）を一酸化炭素及び水素と接触させて、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（ｃ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のアルデヒド基及び反応性炭素− 炭素二重結合を含む前記ポリ（第３アミン）を第１アミン又は第２の第２アミンと反応させて、第２アミン基又は前記第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が、制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含む前記ポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しい前記ポリアミンを生成する段階とを含み、但し（ｃ）の前記還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、前記第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである前記方法。２．前記第１の第２アミン及び前記第２の第２アミンが式ＲＲ’ＮＨ（式中、Ｒ及びＲ’は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択される）により表され、但し前記第１の第２アミンと前記第２の第２アミンは相互に異なり、前記第１アミンは式ＲＮＨ₂（式中、Ｒは上記と同義である）により表される請求項１に記載の方法。３．前記置換脂肪族、置換芳香族又は置換脂環式基上の置換基が、（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅及びＲ₆は独立して水素、脂肪族基、芳香族基及び脂環式基から構成される群から選択され、但しＲ₁及びＲ₂の少なくとも一方とＲ₅ 及びＲ₆の少なくとも一方は水素以外のものであり、Ｒ₄は脂肪族基、芳香族基及び脂環式基から構成される群から選択され、ｍは０〜４の整数であり、ｎは１〜７の整数である）及びその混合物から構成される群から選択される請求項２に記載の方法。４．（ｃ）のアミンが前記第１アミンである請求項１に記載の方法。５．（ｃ）のアミンが前記第２の第２アミンである請求項１に記載の方法。６．前記ポリアミンの合計ペンダントアミン官能基密度が２モル％〜約９０モル％であり、前記第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度が合計ペンダントアミン官能基密度の約５〜約９５％であり、但し前記第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％であり、ペンダント第２アミン基又は前記第２の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％である請求項１に記載の方法。７．（ａ）又は（ｃ）の前記還元的アミノ化がルテニウム含有イミン水素化触媒の存在下で実施される請求項１に記載の方法。８．前記ルテニウム含有イミン水素化触媒がトリルテニウムドデカカルボニルである請求項７に記載の方法。９．(ａ)又は(ｃ)の前記還元的アミノ化がアルカリ金属ホウ水素化物の存在下で実施される請求項１に記載の方法。１０．前記アルカリ金属ホウ水素化物がＮａＢＨ(Ｏ₂ＣＣＨ₃)₃又はＮａＢＨ₃ＣＮである請求項９に記載の方法。１１．（ａ）及び（ｃ）の前記還元的アミノ化が一酸化炭素の存在下で実施される請求項７に記載の方法。１２．（ａ）の前記ポリアルデヒドが、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される請求項１に記載の方法。１３．オレフィン性不飽和を含む前記ポリマーがポリブタジエン及びポリ（エチレンプロピレンジエンモノマー）から構成される群から選択される請求項１２に記載の方法。１４．前記ポリアルデヒド中のアルデヒド基の量が、前記ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される請求項１２に記載の方法。１５．制御された量のアルデヒド基及び反応性炭素−炭素二重結合を含む前記ポリ（第３アミン）中のアルデヒド基の量が、(ｂ)の前記ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される請求項１に記載の方法。１６．制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン又は異なった第３アミン基を含むポリアミンの製造方法であって、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基及び反応性炭素−炭素二重結合を含むポリアルデヒドを、還元的アミノ化すべきペンダントアルデヒド基の百分率に依存する量の第１の第２アミンと接触させて、ポリ（第３アミン）中のペンダント第３アミン基及びペンダントアルデヒド基の和と反応性炭素−炭素二重結合の比が前記ポリアルデド中のペンダントアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しくなるように、制御された量のペンダント第３アミン基、制御された量のペンダントアルデヒド基及び制御された量の反応性炭素−炭素二重結合を含むポリ（第３アミン）を生成する段階と、（ｂ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で（ａ）の前記ポリ（第３アミン）を第１アミン又は第２の第２アミンと接触させて、第２アミン基又は前記第２の第２アミンから誘導される第３アミン基と反応性炭素−炭素二重結合の比が（ａ）の前記ポリ（第３アミン）中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しい前記ポリアミンを生成する段階とを含み、但し（ｂ）の前記還元的アミノ化がアルカリ金属ホウ水素化物の存在下で第１アミンを用いて実施される場合には、前記第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである前記方法。１７．前記第１の第２アミン及び前記第２の第２アミンが式ＲＲ’ＮＨ（式中、Ｒ及びＲ’は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択される）により表され、但し前記第１の第２アミンと前記第２の第２アミンは相互に異なり、前記第１アミンは式ＲＮＨ₂（式中、Ｒは上記と同義である）により表される請求項１６に記載の方法。１８．前記置換脂肪族、置換芳香族又は置換脂環式基上の置換基が式：（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅及びＲ₆は独立して水素、脂肪族基、芳香族基及び脂環式基から構成される群から選択され、但しＲ₁及びＲ₂の少なくとも一方とＲ₅ 及びＲ₆の少なくとも一方は水素以外のものであり、Ｒ₄は脂肪族基、芳香族基及び脂環式基から構成される群から選択され、ｍは０〜４の整数であり、ｎは１〜７の整数である）及びその混合物から構成される群から選択される請求項１７に記載の方法。１９．（ｂ）のアミンが前記第１アミンである請求項１６に記載の方法。２０．（ｂ）のアミンが前記第２の第２アミンである請求項１６に記載の方法。２１．前記ポリアミンの合計ペンダントアミン官能基密度が２モル％〜約９０モル％であり、前記第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度が合計ペンダントアミン官能基密度の約５〜約９５％であり、但し前記第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％であり、ペンダント第２アミン基又は前記第２の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％である請求項１６に記載の方法。２２．（ａ）又は（ｂ）の前記還元的アミノ化がルテニウム含有イミン水素化触媒の存在下で実施される請求項１６に記載の方法。２３．前記ルテニウム含有イミン水素化触媒がトリルテニウムドデカカルボニルである請求項２２に記載の方法。２４．（ａ）又は（ｂ）の前記還元的アミノ化がアルカリ金属ホウ水素化物の存在下で実施される請求項１６に記載の方法。２５．前記アルカリ金属ホウ水素化物がＮａＢＨ（Ｏ₂ＣＣＨ₃）₃又はＮａＢＨ₃ＣＮである請求項２４に記載の方法。２６．（ａ）又は（ｂ）の前記還元的アミノ化が一酸化炭素の存在下で実施される請求項２２に記載の方法。２７．（ａ）の前記ポリアルデヒドが、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される請求項１６に記載の方法。２８．オレフィン性不飽和を含む前記ポリマーがポリブタジエン及びポリ（エチレンプロピレンジエンモノマー）から構成される群から選択される請求項２７に記載の方法。２９．前記ポリアルデヒド中のアルデヒド基の量が、前記ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される請求項２７に記載の方法。３０．制御された量のペンダント第３アミン基と制御された量のペンダント第２アミン基を含むポリアミンの製造方法であって、（ａ）（１）水素とルテニウム含有イミン水素化触媒又は（２）アルカリ金属ホウ水素化物の存在下に還元的アミノ化条件下で制御された量のペンダントアルデヒド基と炭素 −炭素二重結合を含むポリアルデヒド、第１の第２アミン及び第１アミンを接触させて、第３アミン基及び第２アミン基数の和と反応性炭素−炭素二重結合の比が前記ポリアルデヒド中のアルデヒド基と反応性炭素−炭素二重結合の比に本質的に等しいポリ（第２／第３アミン）を生成する段階を含み、前記第１の第２アミンと前記第１アミンのモル比が前記第１の第２アミンと前記第１アミンの相対反応性及びペンダント第３アミン基とペンダント第２アミン基の所望の制御された量に依存し、但し前記還元的アミノ化がアルカリ金属ホウ水素化物の存在下で実施される場合には、前記第１アミンは立体障害脂肪族もしくは脂環式第１アミン又は芳香族第１アミンである前記方法。３１．前記第１の第２アミンが式ＲＲ’ＮＨ（式中、Ｒ及びＲ’は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択される）により表され、前記第１アミンが式ＲＮＨ₂（式中、Ｒは上記と同義である）により表される請求項３０に記載の方法。３２．前記置換脂肪族、置換芳香族又は置換脂環式基上の置換基が式：（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅及びＲ₆は独立して水素、脂肪族基、芳香族基及び脂環式基から構成される群から選択され、但しＲ₁及びＲ₂の少なくとも一方とＲ₅ 及びＲ₆の少なくとも一方は水素以外のものであり、Ｒ₄は脂肪族基、芳香族基及び脂環式基から構成される群から選択され、ｍは０〜４の整数であり、ｎは１〜７の整数である）及びその混合物から構成される群から選択される請求項３１に記載の方法。３３．前記ポリアミンの合計ペンダントアミン官能基密度が２モル％〜約９０モル％であり、前記第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度が合計ペンダントアミン官能基密度の約５〜約９５％であり、但し前記第１の第２アミンから誘導されるペンダント第３アミン基の官能基密度は少なくとも１モル％であり、ペンダント第２アミン基の官能基密度は少なくとも１モル％である請求項３０に記載の方法。３４．前記還元的アミノ化がルテニウム含有イミン水素化触媒の存在下で実施される請求項３０に記載の方法。３５．前記ルテニウム含有イミン水素化触媒がトリルテニウムドデカカルボニルである請求項３４に記載の方法。３６．前記還元的アミノ化がアルカリ金属ホウ水素化物の存在下で実施される請求項３０に記載の方法。３７．前記アルカリ金属ホウ水素化物がＮａＢＨ（Ｏ₂ＣＣＨ₃）₃又はＮａＢＨ₃ ＣＮである請求項３６に記載の方法。３８．前記還元的アミノ化が一酸化炭素の存在下で実施される請求項３４に記載の方法。３９．（ａ）の前記ポリアルデヒドが、オレフィン性不飽和を含むポリマーをヒドロホルミル化触媒の存在下で一酸化炭素及び水素と接触させることにより生成される請求項３０に記載の方法。４０．オレフィン性不飽和を含む前記ポリマーがポリブタジエン及びポリ（エチレンプロピレンジエンモノマー）から構成される群から選択される請求項３９に記載の方法。４１．前記ポリアルデヒド中のアルデヒド基の量が、前記ヒドロホルミル化中に一酸化炭素と水素の消費を制御することにより制御される請求項３９に記載の方法。４２．式：（式中、Ｐ₁を含む反復単位及びＰ₂を含む反復単位は、ヒドロホルミル化及び還元的アミノ化されたオレフィン性不飽和を含むポリマーの反復単位を表し、Ｐ₃ は反応性炭素−炭素二重結合をもつオレフィン性不飽和を含む同一ポリマーの反復単位を表し、Ｒ、Ｒ’及びＲ”は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択され、Ｐ₁ を含む反復単位とＰ₂を含む反復単位の和は、Ｐ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の和の約２〜約９０％であり、Ｐ₂を含む反復単位の数はＰ₁ を含む反復単位とＰ₂を含む反復単位の数の和の約５〜約９５％であり、但しＰ₁ を含む反復単位とＰ₂を含む反復単位の数は、Ｐ₁ を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の数の和の各々少なくとも１％である）の反復単位を含むポリアミン。４３．Ｐ₁を含む反復単位とＰ₂を含む反復単位の和がＰ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の和の約１０〜約８５％である請求項４２に記載のポリアミン。４４．前記置換脂肪族、置換芳香族及び置換脂環式基の置換基が、（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅及びＲ₆は独立して水素、脂肪族基、芳香族基及び脂環式基から構成される群から選択され、但しＲ₁及びＲ₂の少なくとも一方とＲ₅ 及びＲ₆の少なくとも一方は水素以外のものであり、Ｒ₄は脂肪族基、芳香族基及び脂環式基から構成される群から選択され、ｍは０〜４の整数であり、ｎは１〜７の整数である）及びその混合物から構成される群から選択される請求項４２に記載のポリアミン。４５．前記ポリアミンが式：の反復単位を本質的に含まない請求項４２に記載のポリアミン。４６．前記ポリアミンが式：の反復単位を本質的に含まない請求項４２に記載のポリアミン。４７．式：（式中、Ｐ₁を含む反復単位及びＰ₂を含む反復単位は、ヒドロホルミル化及び還元的アミノ化されたオレフィン性不飽和を含むポリマーの反復単位を表し、Ｐ₃ は反応性炭素−炭素二重結合をもつオレフィン性不飽和を含む同一ポリマーの反復単位を表し、Ｒ、Ｒ’、Ｒ”及びＲ’”は独立して脂肪族基、芳香族基、脂環式基、置換脂肪族基、置換芳香族基及び置換脂環式基から構成される群から選択され、但し−ＮＲＲ’は−ＮＲ”Ｒ’”と異なり、Ｐ₁を含む反復単位とＰ₂を含む反復単位の和は、Ｐ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の和の２〜約９０％であり、Ｐ₁を含む反復単位の数はＰ₁を含む反復単位とＰ₂を含む反復単位の数の和の約５〜約９５％であり、但しＰ₁を含む反復単位とＰ₂を含む反復単位の数は、Ｐ₁を含む反復単位とＰ₂を含む単位反復とＰ₃反復単位の数の和の各々少なくとも１％である）の反復単位を含むポリアミン。４８．Ｐ₁を含む反復単位とＰ₂を含む反復単位の和がＰ₁を含む反復単位とＰ₂を含む反復単位とＰ₃反復単位の和の約１０〜約８５％である請求項４７に記載のポリアミン。４９．前記置換脂肪族、置換芳香族及び置換脂環式基の置換基が、（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅及びＲ₆は独立して水素、脂肪族基、芳香族基及び脂環式基から構成される群から選択され、但しＲ₁及びＲ₂の少なくとも一方とＲ₅ 及びＲ₆の少なくとも一方は水素以外のものであり、Ｒ₄は脂肪族基、芳香族基及び脂環式基から構成される群から選択され、ｍは０〜４の整数であり、ｎは１〜７の整数である）及びその混合物から構成される群から選択される請求項４７に記載のポリアミン。５０．前記ポリアミンが式：の反復単位を本質的に含まない請求項４７に記載のポリアミン。[Procedure of Amendment] Article 184-8 of the Patent Act [Submission date] January 4, 1996 [Correction contents] U.S. Pat. No. 4,657,984 discloses ruthenium or rhodium phosphite as a catalyst. Polymer from carbon monoxide, hydrogen, polymeric olefins and secondary amines using A method of making a poly (tertiary amine) is disclosed. This patent identifies these The use of a catalyst facilitates the reaction, and thus the functionality of the internal and vinyl olefin groups. It has been promoted. European Patent Application 0,603,146 describes functional group density control poly (secondary amine) and And its manufacturing method. The secondary amine is a polymer containing olefinic unsaturation. -Catalyzed hydroformylation followed by reductive amination Is done. As described above, there are various conventional techniques for producing the polymer second and third polyamines. Reaction of vinyl olefin with internal olefin under various conditions using various catalysts It teaches the resulting aminomethylation reaction. However, conventional aminomethylation techniques The technique depends on the degree of functionalization of the polyaldehyde or the polyamine produced from the polyaldehyde. No teaching on how to control functional group density, especially the amount of various amine pendant groups Since these reactions do not It is significantly different from the reaction sequence of amination. Using milder reaction conditions, the result was a controlled amount of pendant tertiary Min and pendant secondary amine groups, or controlled amounts of two different pendants. A polymer having a high density of functional groups containing a tertiary amine group is produced, and a polymer soluble in an organic solvent is produced. Functional group density control polyamid containing residual reactive carbon-carbon double bonds to form mer It would be highly desirable if a method of manufacturing a battery could be realized. In accordance with the present invention, a controlled amount of pendant tertiary amine groups and a controlled amount of peptide are provided. A method for the preparation of secondary amines or polyamines containing different tertiary amine groups is provided. The method comprises: (1) hydrogen and a ruthenium-containing imine hydrogenation catalyst or (2) Lucali metal borohydride ) In the presence of a controlled amount of pendant aldehyde groups under reductive amination conditions. And a polyaldehyde containing a reactive carbon-carbon double bond is contacted with a primary secondary amine. The ratio of the tertiary amine group to the reactive carbon-carbon double bond is Poly (tertiary amine) essentially equal to the ratio of dehydrate groups to reactive carbon-carbon double bonds Under conditions of hydroformylation in the presence of a hydroformylation catalyst. Contacting a poly (tertiary amine) containing a reactive carbon-carbon double bond with carbon monoxide and hydrogen. When touched, a porosity containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. Li (tertiary amine) generation step, and (1) hydrogen and ruthenium-containing imine hydrogenation Catalyst or (2) Alkali metal borohydride in the presence of reductive amination conditions. A poly (tertiary amine) containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. ) Is a primary amine or a secondary secondary amine. Secondary amine groups or tertiary amines derived from secondary secondary amines by reaction with amines Amount of aldehyde groups and reactive carbon with controlled ratio of groups to reactive carbon-carbon double bonds Aldehyde groups in poly (tertiary amine) containing carbon-carbon double bond and reactive carbon-carbon Producing a polyamine essentially equivalent to the ratio of elementary double bonds, but controlling Poly (tertiary amine) containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds Of the reductive amination of Pd with primary amines in the presence of alkali metal borohydrides. When applied, the primary amine is a sterically hindered aliphatic or cycloaliphatic primary amine or It is an aromatic primary amine. In one embodiment, the reductive amination is the presence of carbon monoxide. It is carried out below. In another aspect, the polyaldehyde has olefinic unsaturation. Contacting the containing polymer with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst. It is generated by In yet another embodiment, a controlled amount of aldehyde groups And a polyaldehyde or poly (tertiary amine) containing a reactive carbon-carbon double bond The amount of aldehyde groups in the product controls carbon monoxide and hydrogen consumption during hydroformylation. Controlled by Further in accordance with the present invention, a controlled amount of pendant third arm is provided. Containing a controlled amount of pendant secondary amines or different tertiary amine groups with a min group A method for producing a polyamine is provided, the method comprising: (1) hydrogen- and ruthenium-containing imine Hydrogenation catalyst or (2) reductive amination in the presence of alkali metal borohydride A controlled amount of pendant aldehyde groups and reactive carbon-carbon double bonds under Percentage of pendant aldehyde groups to be reductively aminated containing polyaldehydes In a poly (tertiary amine) in contact with an amount of primary secondary amine dependent on And the reactive carbon-carbon double bond of the tertiary amine group and the pendant aldehyde group Ratio of the reactive carbon-carbon double bond to the pendant aldehyde group in polyaldedo A controlled amount of pendant tertiary amine groups, controlled to be essentially equal to the ratio Controlled amounts of pendant aldehyde groups and controlled amounts of reactive carbon-carbon double bonds. And a step of producing poly (tertiary amine) containing hydrogen, and (1) hydrogen and ruthenium-containing iron. Reductive amination in the presence of Min hydrogenation catalyst or (2) alkali metal borohydride Contacting the poly (tertiary amine) with a primary amine or a secondary secondary amine under conditions, Reactive carbon with a secondary amine group or a tertiary amine group derived from a secondary secondary amine- The carbon double bond ratio is The ratio of reactive carbon-carbon double bonds to the aldehyde groups in And a reductive amination is an alkali metal borohydride. Primary amine is a sterically hindered fat when carried out with a primary amine in the presence of Group or alicyclic primary amine or aromatic primary amine. In one aspect, the return Native amination is carried out in the presence of carbon monoxide. In another embodiment, polyal Dehydrates polymers containing olefinic unsaturation in the presence of hydroformylation catalysts. It is produced by contacting with carbon monoxide and hydrogen. In another aspect The functional group density of polyaldehyde, that is, in a polymer containing olefinic unsaturation The mole percentage of carbon-carbon double bonds hydroformylated to aldehyde groups is It is controlled by controlling the consumption of carbon monoxide and hydrogen during Droformylation. Further in accordance with the present invention, a controlled amount of pendant tertiary amine groups and a controlled amount of A method of making a polyamine comprising pendant secondary amine groups of is provided, the method comprising: (1) Hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal borohydride Controlled amount of pendant aldehyde groups in the presence of halides under reductive amination conditions And a carbon-carbon double bond Contacting the containing polyaldehyde, the first secondary amine and the primary amine to form a tertiary amine. Of the total number of amine groups and secondary amine groups and the ratio of reactive carbon-carbon double bonds are polyaldehydes. In the poly (secondary group) essentially equal to the ratio of the aldehyde groups in the reactive carbon-carbon double bond / Tertiary amine). Detailed description of the invention The first aspect of the present invention is a controlled amount of pendant tertiary amine groups with a controlled amount. For the production of polyamines containing a quantity of pendant secondary amines or different tertiary amine groups Regarding the method, the method comprises: (a) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) Controlled under reductive amination conditions in the presence of alkali metal borohydride Polyaldehyde containing a quantity of pendant aldehyde groups and a reactive carbon-carbon double bond Contacting the primary amine with the secondary amine to react with the tertiary amine group and the reactive carbon-carbon double bond. The ratio of s is essentially dependent on the ratio of aldehyde groups and reactive carbon-carbon double bonds in the polyaldehyde. To produce a poly (tertiary amine) which is substantially equal to (b) a hydroformylation catalyst Poly (containing a reactive carbon-carbon double bond under hydroformylation conditions in the presence of 3 amines) with carbon monoxide and hydrogen to produce a controlled amount of aldehyde groups and And a poly (tertiary amine) containing a reactive carbon-carbon double bond, (c ) (1) Hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal borate Controlled amount of aldehyde groups and reaction under reductive amination conditions in the presence of hydride A poly (tertiary amine) containing a reactive carbon-carbon double bond as a primary amine From a secondary amine group or secondary secondary amine by reacting with a secondary amine group or a secondary secondary amine. The ratio of derivatized tertiary amine groups and reactive carbon-carbon double bonds is controlled by the amount of alkanes. Aldehy in a poly (tertiary amine) containing a dehydration group and a reactive carbon-carbon double bond A step of producing a polyamine having essentially the same ratio of reactive groups to reactive carbon-carbon double bonds And a reductive amination of (c) in the presence of an alkali metal borohydride. When practiced with a primary amine, the primary amine is a sterically hindered aliphatic or It is an alicyclic primary amine or an aromatic primary amine. According to the method of the first aspect of the present invention, the polyaldehyde of (a) is olefinic. Polymers containing unsaturation were treated with carbon monoxide and hydrogen in the presence of hydroformylation catalysts. It is generated by bringing them into contact. In addition, the reductive amination involves hydrogen and ruthenium. When carried out in the presence of an imine-containing hydrogenation catalyst, the reducing reductive of (a) or (c) The amination can optionally be carried out in the presence of carbon monoxide. During reductive amination When carbon monoxide is present, the molar ratio of carbon monoxide to hydrogen is less than about 0.15: 1, Preferably less than about 0.1: 1, optimally less than about 0.05: 1. A second aspect of the invention is a controlled amount of pendant tertiary amine groups and a controlled amount of Of pendant secondary amines or polyamines containing different tertiary amine groups (A) (1) hydrogen and a ruthenium-containing imine hydrogenation catalyst, or 2) Controlled amount under reductive amination conditions in the presence of alkali metal borohydride. Containing pendant aldehyde groups and reactive carbon-carbon double bond Of the first amount depending on the percentage of pendant aldehyde groups to be reductively aminated. The pendant tertiary amine group in the poly (tertiary amine) by contact with the secondary amine of And the pendant aldehyde group and the ratio of reactive carbon-carbon double bond Essentially equal to the ratio of pendant aldehyde groups in the and reactive carbon-carbon double bond So that a controlled amount of pendant tertiary amine groups, a controlled amount of pendan Poly (3rd group) containing a trialdehyde group and a controlled amount of reactive carbon-carbon double bonds. (B) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst; (A) under reductive amination conditions in the presence of a medium or (2) an alkali metal borohydride. Contacting the poly (tertiary amine) of (1) with a primary amine or a secondary amine, Induced from amine group or secondary secondary amine The ratio of the introduced tertiary amine group to the reactive carbon-carbon double bond is (a) poly (tertiary amine). The ratio of reactive carbon-carbon double bonds to aldehyde groups in The step of producing an amine, provided that the reductive amination of (b) is When carried out with a primary amine in the presence of a hydride, the primary amine is Physically impaired aliphatic or alicyclic primary amine or aromatic primary amine. According to the method of the second aspect of the invention, the polyaldehyde is olefinically unsaturated. Of a polymer containing carbon with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst. It is generated by In addition, the reductive amination of (a) or (b) with hydrogen When carried out in the presence of a ruthenium-containing imine hydrogenation catalyst, the reductive amino The conversion can optionally be carried out in the presence of carbon monoxide. Monoxide during reductive amination When carbon is present, the molar ratio of carbon monoxide to hydrogen is less than about 0.15: 1, preferably Or less than about 0.1: 1, optimally less than about 0.05: 1. A third aspect of the invention is a controlled amount of pendant tertiary amine groups and a controlled amount of And a method for producing a polyamine containing pendant secondary amine groups of ) (1) Hydrogen In one aspect, the polyaldehyde can be recovered prior to reductive amination. Poly When recovering the aldehyde, it can be recovered by any conventional recovery method. For example, when carrying out the hydroformylation reaction in the presence of a solvent (for example, toluene), Reduce the amount of solvent in the reaction mixture and slowly add methanol while stirring the mixture. And the polyaldehyde is precipitated. The polymer is then recovered and reconstituted in the original solvent. Dissolve and reprecipitate with methanol. In this way, the purified polyaldehyde is recovered. be able to.Reductive amination Reductive amination is carried out in a suitable solvent in the presence of a ruthenium-containing imine hydrogenation catalyst. Reacting the polyaldehyde with a primary secondary amine and hydrogen at Reacting the polyaldehyde with a primary and secondary amine in the presence of a polymetal borohydride. It is carried out by Poly (tertiary amine) produced by the method of the present invention Has a ratio of tertiary amine groups to reactive carbon-carbon double bonds in aldehydes in polyaldehydes. Essentially equal to the ratio of hydrido groups to reactive carbon-carbon double bonds. Poly (3rd order) containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. The reductive amination of The poly (tertiary amine) was reacted with a poly (tertiary amine) in a suitable solvent in the presence of a hydrogen-containing imine catalyst. Reacting with a primary amine or secondary secondary amine and hydrogen, or alkali metal borohydride The poly (tertiary amine) in the presence of hydride to a primary amine or a secondary amine Is carried out by reacting with alkali metal borohydride. When carried out with a primary amine in the presence of a halide, the primary amine is sterically hindered. It is an aliphatic or alicyclic primary amine or an aromatic primary amine. In the method of the present invention The polyamines produced by are derived from secondary amine groups or secondary secondary amines. Amount of aldehyde groups with controlled ratio of tertiary amine groups to reactive carbon-carbon double bonds And an aldehyde group in a poly (tertiary amine) containing a reactive carbon-carbon double bond. Essentially equal to the ratio of reactive carbon-carbon double bonds. The functional group density of the polyamine and / or poly (tertiary amine) depends on the polyaldehyde and And / or the functional group density of the aldehyde groups in the poly (tertiary amine). Therefore , The functional group density of the polyamine is the total pendant amine functional group density Carbon in Polymers Containing Olefinic Unsaturation Used to Make Dehydrates- Based on carbon double bond level Then, it can be easily controlled to be in the range of 2 mol% to about 90 mol%. Therefore, the total pendant amine functional group density in the polyamine is 2 mol% to about 90 mol%, preferably depending on the specific functional group density desired. It can be any value in the range of about 10 mol% to about 85 mol%. First in polyamines The functional group density of pendant tertiary amine groups derived from the secondary amine of About 5 to about 95% of the functional groups of the amines, but derived from the primary and secondary amines. The functional group density of the pendant tertiary amine group is at least 1 mol%, Of secondary amine groups or pendant tertiary amine groups derived from secondary secondary amine groups The functional group density is at least 1 mol%. Therefore, the total pendant amine functional group Is derived from pendant secondary amine groups or secondary amines in polyamines Derived from the functional group density of the pendant tertiary amine groups.The scope of the claims 1. A controlled amount of pendant tertiary amine groups and a controlled amount of pendant secondary amine groups. A process for the preparation of a polyamine containing amines or different tertiary amine groups, the method comprising: (A) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphide C. A controlled amount of pendant aldene under reductive amination conditions in the presence of hydride. A polyaldehyde containing a hydrido group and a reactive carbon-carbon double bond is used as a primary secondary amine. And the ratio of the tertiary amine group to the reactive carbon-carbon double bond is adjusted to The poly (essentially equal to the ratio of the aldehyde groups in the hydride and the reactive carbon-carbon double bonds Generating a tertiary amine). (B) reactive carbon under hydroformylation conditions in the presence of a hydroformylation catalyst Contacting said poly (tertiary amine) containing carbon double bonds with carbon monoxide and hydrogen , Poly (3rd group) containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. Amine) production step, (C) (1) Hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphate A controlled amount of aldehyde groups under reductive amination conditions in the presence of hydride and Reactive carbon- The poly (tertiary amine) containing a carbon double bond is replaced with a primary amine or a secondary amine. Reacting with a secondary amine group or a tertiary amine derived from said secondary secondary amine. The ratio of reactive groups to reactive carbon-carbon double bonds is controlled by a controlled amount of aldehyde groups and reaction. Reactive with aldehyde groups in the poly (tertiary amine) containing a reactive carbon-carbon double bond Forming said polyamine which is essentially equal to the ratio of carbon-carbon double bonds. However, the reductive amination of (c) is carried out in the presence of an alkali metal borohydride. When practiced with a monoamine, the primary amine is a sterically hindered aliphatic or Is an alicyclic primary amine or aromatic primary amine. 2. The first secondary amine and the second secondary amine are of the formula RR'NH (wherein R And R'independently represent an aliphatic group, an aromatic group, an alicyclic group, a substituted aliphatic group or a substituted aromatic group. Selected from the group consisting of a group and a substituted alicyclic group, provided that The first secondary amine and the second secondary amine are different from each other and the primary amine has the formula RNH₂The method according to claim 1, which is represented by the formula: wherein R is as defined above. . 3. The substituent on the substituted aliphatic, substituted aromatic or substituted alicyclic group is (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The described method. 4. The method of claim 1, wherein the amine of (c) is the primary amine. 5. The method of claim 1, wherein the amine of (c) is the second secondary amine. 6. The total pendant amine functional group density of the polyamine is 2 mol% to about 90 mol. %, The functionality of the pendant tertiary amine group derived from said first secondary amine The group density is about 5 to about 95% of the total pendant amine functional group density, provided that Pendant tertiary amine derived from secondary amine of 1 The functional group density of the min group is at least 1 mol%, and the pendant secondary amine group or The functional group density of the pendant tertiary amine group derived from the second secondary amine is low. The method according to claim 1, wherein the amount is at least 1 mol%. 7. The reductive amination of (a) or (c) is a ruthenium-containing imine hydrogenation catalyst The method according to claim 1, which is carried out in the presence of 8. The ruthenium-containing imine hydrogenation catalyst is triruthenium dodecacarbonyl. The method of claim 7. 9. The reductive amination of (a) or (c) is carried out in the presence of an alkali metal borohydride. The method according to claim 1, wherein the method is performed. 10. The alkali metal borohydride is NaBH (O₂CCH_Three)_ThreeOr NaBH_ThreeC The method according to claim 9, wherein N is N. 11. The reductive amination of (a) and (c) is carried out in the presence of carbon monoxide. The method according to claim 7, wherein 12. The polyaldehyde of (a) comprises a polymer containing olefinic unsaturation. Produced by contacting with carbon monoxide and hydrogen in the presence of Droformylation catalyst The method of claim 1, wherein the method is performed. 13. The polymer containing olefinic unsaturation is polybutane Selected from the group consisting of diene and poly (ethylene propylene diene monomer) 13. The method of claim 12 selected. 14． The amount of aldehyde groups in the polyaldehyde during the hydroformylation The method according to claim 12, which is controlled by controlling the consumption of carbon monoxide and hydrogen. Law. 15. The above-mentioned groups containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. The amount of aldehyde groups in the poly (tertiary amine) has been determined during the hydroformylation of (b). The method of claim 1 controlled by controlling the consumption of carbon oxides and hydrogen. 16. Controlled amount of pendant tertiary amine group and controlled amount of pendant secondary A method of making an amine or a polyamine containing different tertiary amine groups, the method comprising: (A) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphide C. A controlled amount of pendant aldene under reductive amination conditions in the presence of hydride. Reductive amination of polyaldehydes containing hydrido groups and reactive carbon-carbon double bonds. Contacting with a percentage of primary and secondary amines depending on the percentage of pendant aldehyde groups to be The pendant tertiary amine group and the pendant aldene in the poly (tertiary amine) Hydr group And the ratio of the reactive carbon-carbon double bond is equal to the pendant alde Controlled to be essentially equal to the ratio of the hydrido group to the reactive carbon-carbon double bond. A controlled amount of pendant tertiary amine groups, a controlled amount of pendant aldehyde groups and a controlled amount. A step for producing a poly (tertiary amine) containing a controlled amount of reactive carbon-carbon double bonds Floor and (B) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphate (C) the poly (tertiary amine) of (a) under reductive amination conditions in the presence of hydride With a primary amine or a secondary secondary amine to form a secondary amine group or the secondary amine The ratio of the tertiary amine group derived from the secondary amine to the reactive carbon-carbon double bond is (a ) The ratio of the aldehyde groups in the poly (tertiary amine) to the reactive carbon-carbon double bond Producing a polyamine essentially equal to Primary amination was carried out with primary amines in the presence of alkali metal borohydrides. The primary amine is a sterically hindered aliphatic or cycloaliphatic primary amine or The foregoing method which is an aromatic primary amine. 17． The first secondary amine and the second secondary amine are of the formula RR'NH (wherein R and R'are independently an aliphatic group, Consisting of aromatic group, alicyclic group, substituted aliphatic group, substituted aromatic group and substituted alicyclic group Is selected from the group consisting of: The two amines are different from each other and the primary amine is of the formula RNH₂(In the formula, R has the same meaning as above. 17. The method of claim 16 represented by 18. The substituent on the substituted aliphatic, substituted aromatic or substituted alicyclic group has the formula: (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The method described in. 19. The method of claim 16, wherein the amine of (b) is the primary amine. 20. The method of claim 16, wherein the amine of (b) is the second secondary amine. 21. The total pendant amine functional group density of the polyamine is 2 mol% to about 90 mol%. % Of the pendant tertiary amine group derived from said first secondary amine The functional group density is about 5 to about 95% of the total pendant amine functional group density, provided that The functional group density of the pendant tertiary amine group derived from the primary and secondary amines is low Both are 1 mol% and are derived from the pendant secondary amine group or the secondary secondary amine. The functional group density of the derived pendant tertiary amine groups is at least 1 mol%. Item 16. The method according to Item 16. 22. The reductive amination of (a) or (b) is a ruthenium-containing imine hydrogenation catalyst. The method according to claim 16, which is carried out in the presence of a medium. 23. The ruthenium-containing imine hydrogenation catalyst is triruthenium dodecacarbonyl. 23. The method of claim 22, wherein 24. The reductive amination of (a) or (b) is the presence of an alkali metal borohydride. 17. The method according to claim 16, which is performed ex situ. 25. The alkali metal borohydride is NaBH (O₂C CH_Three)_ThreeOr NaBH_Three25. The method of claim 24, which is CN. 26. The reductive amination of (a) or (b) is carried out in the presence of carbon monoxide. 23. The method of claim 22, wherein 27. The polyaldehyde of (a) comprises a polymer containing olefinic unsaturation. Produced by contacting with carbon monoxide and hydrogen in the presence of Droformylation catalyst The method of claim 16, wherein the method is performed. 28. The polymers containing olefinic unsaturation include polybutadiene and poly (ethylene). Len propylene diene monomer) according to claim 27 selected from the group consisting of The described method. 29. The amount of aldehyde groups in the polyaldehyde during the hydroformylation The method according to claim 27, which is controlled by controlling the consumption of carbon monoxide and hydrogen. Law. 30. Controlled amount of pendant tertiary amine group and controlled amount of pendant secondary A method for producing a polyamine containing an amine group, comprising: (A) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphide C. A controlled amount of pendant aldene under reductive amination conditions in the presence of hydride. Hydro group and carbon Contacting a polyaldehyde containing a carbon double bond, a primary secondary amine and a primary amine The ratio of the number of tertiary amine groups and the number of secondary amine groups and the reactive carbon-carbon double bond. Essentially depends on the ratio of the aldehyde group and the reactive carbon-carbon double bond in the polyaldehyde. Producing a substantially equal poly (second / tertiary amine), said first second amine The molar ratio of the amine and the primary amine is relative to the primary secondary amine and the primary amine. Reactivity and desired control of pendant tertiary amine groups and pendant secondary amine groups Depending on the amount of the reductive amination, in the presence of alkali metal borohydride. When practiced, the primary amine is a sterically hindered aliphatic or cycloaliphatic primary amine. Or a primary aromatic amine. 31. The first and second amines are of the formula RR'NH, where R and R'are independently From aromatic groups, aromatic groups, alicyclic groups, substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups Selected from the group consisting of), wherein the primary amine is of the formula RNH₂(formula 31. The method according to claim 30, wherein R is as defined above. 32. The substituent on the substituted aliphatic, substituted aromatic or substituted alicyclic group has the formula: (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ˜7) and mixtures thereof. The method described in. 33. The total pendant amine functional group density of the polyamine is 2 mol% to about 90 mol%. % Of the pendant tertiary amine group derived from said first secondary amine The functional group density is about 5 to about 95% of the total pendant amine functional group density, provided that The functional group density of the pendant tertiary amine group derived from the primary and secondary amines is low And the functional group density of the pendant secondary amine group is at least 1 mol%. 31. The method of claim 30, which is%. 34. The reductive amination is ruthenium-containing imine hydrogenation 31. The method according to claim 30, which is carried out in the presence of a catalyst. 35. The ruthenium-containing imine hydrogenation catalyst is triruthenium dodecacarbonyl. 35. The method of claim 34, wherein 36. A contract in which the reductive amination is carried out in the presence of an alkali metal borohydride. The method according to claim 30. 37. The alkali metal borohydride is NaBH (O₂CCH_Three)_ThreeOr NaBH_Three 37. The method of claim 36, which is CN. 38. The reductive amination is carried out in the presence of carbon monoxide. the method of. 39. The polyaldehyde of (a) comprises a polymer containing olefinic unsaturation. Produced by contacting with carbon monoxide and hydrogen in the presence of Droformylation catalyst 31. The method of claim 30, wherein the method is performed. 40. The polymers containing olefinic unsaturation include polybutadiene and poly (ethylene). 40. A propylene propylene diene monomer) according to claim 39. The described method. 41. The amount of aldehyde groups in the polyaldehyde during the hydroformylation Controls carbon monoxide and hydrogen consumption 40. The method of claim 39 controlled by. 42. formula: (In the formula, P₁A repeating unit containing P and P₂Repeating units containing Representing a repeating unit of a polymer containing natively aminated olefinic unsaturation, P_Three Is the reaction of the same polymer containing olefinic unsaturation with reactive carbon-carbon double bonds. R, R'and R "independently represent an aliphatic group, an aromatic group, an alicyclic group, or a unit. Selected from the group consisting of substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups, P₁ A repeating unit containing P and₂The sum of repeating units containing₁A repeating unit containing P and₂Anti-including Return unit and P_ThreeAbout 2 to about 90% of the sum of repeating units, P₂The number of repeating units containing₁ A repeating unit containing P and₂About 5 to about 95% of the total number of repeating units including P₁ A repeating unit containing P and₂The number of repeating units containing₁ A repeating unit containing P and₂A repeating unit containing P and_ThreeAt least one of each of the number of repeating units %) Of polyamines. 43. P₁A repeating unit containing P and₂Is the sum of repeating units containing₁A repeating unit containing P and₂To Including repeating unit and P_Three43. The about 42 to about 85% of the sum of repeating units. Polyamine. 44. The substituted aliphatic, substituted aromatic and substituted alicyclic group substituents, (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The polyamine according to. 45. The polyamine has the formula: 43. The polyamine of claim 42 which is essentially free of repeating units of. 46. The polyamine has the formula: 43. The polyamine of claim 42 which is essentially free of repeating units of. 47. formula: (In the formula, P₁A repeating unit containing P and P₂Repeating units containing Representing a repeating unit of a polymer containing natively aminated olefinic unsaturation, P_Three Is the reaction of the same polymer containing olefinic unsaturation with reactive carbon-carbon double bonds. Represents a subunit, and R, R ', R "and R'" are independently an aliphatic group, an aromatic group, or an alicyclic group. Selected from the group consisting of formula groups, substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups However, -NRR 'is different from -NR "R'", and₁A repeating unit containing P and₂Including The sum of repeating units is P₁A repeating unit containing P and₂A repeating unit containing P and_ThreeSum of repeating units 2 to about 90% of P,₁The number of repeating units containing₁A repeating unit containing P and₂Including It is about 5 to about 95% of the total number of repeating units, provided that P₁A repeating unit containing P and₂Including The number of repeating units is P₁A repeating unit containing P and₂Unit repeats including P and_ThreeNumber of repeating units Of at least 1% of each of the above). 48. P₁A repeating unit containing P and₂Is the sum of repeating units containing₁A repeating unit containing P and₂To Including repeating unit and P_Three48. The sum of repeating units of about 10 to about 85% of claim 47. Polyamine. 49. The substituted aliphatic, substituted aromatic and substituted alicyclic group substituents, (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The polyamine according to. 50. The polyamine has the formula: 48. The polyamine of claim 47 which is essentially free of repeating units of.

───────────────────────────────────────────────────── フロントページの続き (81)指定国ＥＰ(ＡＴ，ＢＥ，ＣＨ，ＤＥ，ＤＫ，ＥＳ，ＦＲ，ＧＢ，ＧＲ，ＩＥ，ＩＴ，ＬＵ，ＭＣ，ＮＬ，ＰＴ，ＳＥ)，ＯＡ(ＢＦ，ＢＪ，ＣＦ，ＣＧ，ＣＩ，ＣＭ，ＧＡ，ＧＮ，ＭＬ，ＭＲ，ＮＥ，ＳＮ，ＴＤ，ＴＧ)，ＡＰ(ＫＥ，ＭＷ，ＳＤ，ＳＺ)，ＡＭ，ＡＵ，ＢＢ，ＢＧ，ＢＲ，ＢＹ，ＣＡ，ＣＮ，ＣＺ，ＥＥ，ＦＩ，ＧＥ，ＨＵ，ＪＰ，ＫＧ，ＫＲ，ＫＺ，ＬＫ，ＬＲ，ＬＴ，ＬＶ，ＭＤ，ＭＧ，ＭＮ，ＮＯ，ＮＺ，ＰＬ，ＲＯ，ＲＵ，ＳＩ，ＳＫ，ＴＪ，ＴＴ，ＵＡ，ＵＺ，ＶＮ────────────────────────────────────────────────── ─── Continuation of front page (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, M C, NL, PT, SE), OA (BF, BJ, CF, CG , CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (KE, MW, SD, SZ), AM, AU, BB, BG, BR, BY, CA, CN, CZ, E E, FI, GE, HU, JP, KG, KR, KZ, LK , LR, LT, LV, MD, MG, MN, NO, NZ, PL, RO, RU, SI, SK, TJ, TT, UA, U Z, VN

Claims

[Claims] 1. A controlled amount of pendant tertiary amine groups and a controlled amount of pendant secondary amine groups. A process for the preparation of a polyamine containing amines or different tertiary amine groups, the method comprising: (A) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphide C. A controlled amount of pendant aldene under reductive amination conditions in the presence of hydride. A polyaldehyde containing a hydrido group and a reactive carbon-carbon double bond is used as a primary secondary amine. And the ratio of the tertiary amine group to the reactive carbon-carbon double bond is adjusted to A poly (substantially equal to the ratio of the aldehyde groups in the hydride to the reactive carbon-carbon double bond Generating a tertiary amine). (B) reactive carbon under hydroformylation conditions in the presence of a hydroformylation catalyst Contacting said poly (tertiary amine) containing carbon double bonds with carbon monoxide and hydrogen , Poly (3rd group) containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. Amine) production step, (C) (1) Hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphate A controlled amount of aldehyde groups under reductive amination conditions in the presence of hydride and Reactive carbon- The poly (tertiary amine) containing a carbon double bond is replaced with a primary amine or a secondary amine. Reacting with a secondary amine group or a tertiary amine derived from said secondary secondary amine. The ratio of reactive groups to reactive carbon-carbon double bonds is controlled by a controlled amount of aldehyde groups and reaction. Reactive with aldehyde groups in the poly (tertiary amine) containing a reactive carbon-carbon double bond Forming the polyamine substantially equal to the ratio of carbon-carbon double bonds. However, the reductive amination of (c) is carried out in the presence of an alkali metal borohydride. When practiced with a monoamine, the primary amine is a sterically hindered aliphatic or Is an alicyclic primary amine or aromatic primary amine. 2. The first secondary amine and the second secondary amine are of the formula RR'NH (wherein R And R'independently represent an aliphatic group, an aromatic group, an alicyclic group, a substituted aliphatic group or a substituted aromatic group. Selected from the group consisting of a group and a substituted alicyclic group, provided that The first secondary amine and the second secondary amine are different from each other and the primary amine has the formula RNH₂The method according to claim 1, which is represented by the formula: wherein R is as defined above. . 3. The substituent on the substituted aliphatic, substituted aromatic or substituted alicyclic group is (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The described method. 4. The method of claim 1, wherein the amine of (c) is the primary amine. 5. The method of claim 1, wherein the amine of (c) is the second secondary amine. 6. The total pendant amine functional group density of the polyamine is 2 mol% to about 90 mol. %, The functionality of the pendant tertiary amine group derived from said first secondary amine The group density is about 5 to about 95% of the total pendant amine functional group density, provided that Pendant tertiary amine derived from secondary amine of 1 The functional group density of the min group is at least 1 mol%, and the pendant secondary amine group or The functional group density of the pendant tertiary amine group derived from the second secondary amine is low. The method according to claim 1, wherein the amount is at least 1 mol%. 7. The reductive amination of (a) or (c) is a ruthenium-containing imine hydrogenation catalyst The method according to claim 1, which is carried out in the presence of 8. The ruthenium-containing imine hydrogenation catalyst is triruthenium dodecacarbonyl. The method of claim 7. 9. The reductive amination of (a) or (c) is carried out in the presence of an alkali metal borohydride. The method according to claim 1, wherein the method is performed. 10. The alkali metal borohydride is NaBH (O₂CCH_Three)_ThreeOr NaBH_ThreeC The method according to claim 9, wherein N is N. 11. The reductive amination of (a) and (c) is carried out in the presence of carbon monoxide. The method according to claim 7, wherein 12. The polyaldehyde of (a) comprises a polymer containing olefinic unsaturation. Produced by contacting with carbon monoxide and hydrogen in the presence of Droformylation catalyst The method of claim 1, wherein the method is performed. 13. The polymer containing olefinic unsaturation is polybutane Selected from the group consisting of diene and poly (ethylene propylene diene monomer) 13. The method of claim 12 selected. 14． The amount of aldehyde groups in the polyaldehyde during the hydroformylation The method according to claim 12, which is controlled by controlling the consumption of carbon monoxide and hydrogen. Law. 15. The above-mentioned groups containing a controlled amount of aldehyde groups and reactive carbon-carbon double bonds. The amount of aldehyde groups in the poly (tertiary amine) has been determined during the hydroformylation of (b). The method of claim 1 controlled by controlling the consumption of carbon oxides and hydrogen. 16. Controlled amount of pendant tertiary amine group and controlled amount of pendant secondary A method of making an amine or a polyamine containing different tertiary amine groups, the method comprising: (A) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphide C. A controlled amount of pendant aldene under reductive amination conditions in the presence of hydride. Reductive amination of polyaldehydes containing hydrido groups and reactive carbon-carbon double bonds. Contacting with a percentage of primary and secondary amines depending on the percentage of pendant aldehyde groups to be The pendant tertiary amine group and the pendant aldene in the poly (tertiary amine) Hydr group And the ratio of the reactive carbon-carbon double bond is equal to the pendant alde Controlled to be substantially equal to the ratio of the hydrido group to the reactive carbon-carbon double bond. A controlled amount of pendant tertiary amine groups, a controlled amount of pendant aldehyde groups and a controlled amount. A step for producing a poly (tertiary amine) containing a controlled amount of reactive carbon-carbon double bonds Floor and (B) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphate (C) the poly (tertiary amine) of (a) under reductive amination conditions in the presence of hydride With a primary amine or a secondary secondary amine to form a secondary amine group or the secondary amine The ratio of the tertiary amine group derived from the secondary amine to the reactive carbon-carbon double bond is (a ) The ratio of the aldehyde groups in the poly (tertiary amine) to the reactive carbon-carbon double bond Producing said polyamine substantially equal to However, when the reductive amination of (b) is carried out in the presence of an alkali metal borohydride, When practiced with mines, the primary amine is a sterically hindered aliphatic or fatty The above method, which is a cyclic primary amine or an aromatic primary amine. 17． The first secondary amine and the second secondary amine are of the formula RR'NH (wherein R and R'are independently an aliphatic group, Consisting of aromatic group, alicyclic group, substituted aliphatic group, substituted aromatic group and substituted alicyclic group Is selected from the group consisting of: The two amines are different from each other and the primary amine is of the formula RNH₂(In the formula, R has the same meaning as above. 17. The method of claim 16 represented by 18. The substituent on the substituted aliphatic, substituted aromatic or substituted alicyclic group has the formula: (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The method described in. 19. The method of claim 16, wherein the amine of (b) is the primary amine. 20. The method of claim 16, wherein the amine of (b) is the second secondary amine. 21. The total pendant amine functional group density of the polyamine is 2 mol% to about 90 mol%. % Of the pendant tertiary amine group derived from said first secondary amine The functional group density is about 5 to about 95% of the total pendant amine functional group density, provided that The functional group density of the pendant tertiary amine group derived from the primary and secondary amines is low Both are 1 mol% and are derived from the pendant secondary amine group or the secondary secondary amine. The functional group density of the derived pendant tertiary amine groups is at least 1 mol%. Item 16. The method according to Item 16. 22. The reductive amination of (a) or (b) is a ruthenium-containing imine hydrogenation catalyst. The method according to claim 16, which is carried out in the presence of a medium. 23. The ruthenium-containing imine hydrogenation catalyst is triruthenium dodecacarbonyl. 23. The method of claim 22, wherein 24. The reductive amination of (a) or (b) is the presence of an alkali metal borohydride. 17. The method according to claim 16, which is performed ex situ. 25. The alkali metal borohydride is NaBH (O₂C CH_Three)_ThreeOr NaBH_Three25. The method of claim 24, which is CN. 26. The reductive amination of (a) or (b) is carried out in the presence of carbon monoxide. 23. The method of claim 22, wherein 27. The polyaldehyde of (a) comprises a polymer containing olefinic unsaturation. Produced by contacting with carbon monoxide and hydrogen in the presence of Droformylation catalyst The method of claim 16, wherein the method is performed. 28. The polymers containing olefinic unsaturation include polybutadiene and poly (ethylene). Len propylene diene monomer) according to claim 27 selected from the group consisting of The described method. 29. The amount of aldehyde groups in the polyaldehyde during the hydroformylation The method according to claim 27, which is controlled by controlling the consumption of carbon monoxide and hydrogen. Law. 30. Controlled amount of pendant tertiary amine group and controlled amount of pendant secondary A method for producing a polyamine containing an amine group, comprising: (A) (1) hydrogen and ruthenium-containing imine hydrogenation catalyst or (2) alkali metal phosphide C. A controlled amount of pendant aldene under reductive amination conditions in the presence of hydride. Hydro group and carbon Contacting a polyaldehyde containing a carbon double bond, a primary secondary amine and a primary amine The ratio of the number of tertiary amine groups and the number of secondary amine groups and the reactive carbon-carbon double bond. Is substantially equal to the ratio of the aldehyde group in the polyaldehyde and the reactive carbon-carbon double bond. Producing a substantially equal poly (second / tertiary amine), said first second amine The molar ratio of the amine and the primary amine is relative to the primary secondary amine and the primary amine. Reactivity and desired control of pendant tertiary amine groups and pendant secondary amine groups Depending on the amount of the reductive amination, in the presence of alkali metal borohydride. When practiced, the primary amine is a sterically hindered aliphatic or cycloaliphatic primary amine. Or a primary aromatic amine. 31. The first and second amines are of the formula RR'NH, where R and R'are independently From aromatic groups, aromatic groups, alicyclic groups, substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups Selected from the group consisting of), wherein the primary amine is of the formula RNH₂(formula 31. The method according to claim 30, wherein R is as defined above. 32. The substituent on the substituted aliphatic, substituted aromatic or substituted alicyclic group has the formula: (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ˜7) and mixtures thereof. The method described in. 33. The total pendant amine functional group density of the polyamine is 2 mol% to about 90 mol%. % Of the pendant tertiary amine group derived from said first secondary amine The functional group density is about 5 to about 95% of the total pendant amine functional group density, provided that The functional group density of the pendant tertiary amine group derived from the primary and secondary amines is low And the functional group density of the pendant secondary amine group is at least 1 mol%. 31. The method of claim 30, which is%. 34. The reductive amination is ruthenium-containing imine hydrogenation 31. The method according to claim 30, which is carried out in the presence of a catalyst. 35. The ruthenium-containing imine hydrogenation catalyst is triruthenium dodecacarbonyl. 35. The method of claim 34, wherein 36. A contract in which the reductive amination is carried out in the presence of an alkali metal borohydride. The method according to claim 30. 37. The alkali metal borohydride is NaBH (O₂CCH_Three)_ThreeOr NaBH_Three 37. The method of claim 36, which is CN. 38. The reductive amination is carried out in the presence of carbon monoxide. the method of. 39. The polyaldehyde of (a) comprises a polymer containing olefinic unsaturation. Produced by contacting with carbon monoxide and hydrogen in the presence of Droformylation catalyst 31. The method of claim 30, wherein the method is performed. 40. The polymers containing olefinic unsaturation include polybutadiene and poly (ethylene). 40. A propylene propylene diene monomer) according to claim 39. The described method. 41. The amount of aldehyde groups in the polyaldehyde during the hydroformylation 40. The method of claim 39, controlled by controlling the consumption of carbon monoxide and hydrogen. Law. 42. A polyamine produced by the method of claim 1. 43. A polyamine produced by the method of claim 16. 44. A polyamine produced by the method of claim 30. 45. formula: (In the formula, P₁A repeating unit containing P and P₂Repeating units containing Representing a repeating unit of a polymer containing natively aminated olefinic unsaturation, P_Three Is the reaction of the same polymer containing olefinic unsaturation with reactive carbon-carbon double bonds. R, R'and R "independently represent an aliphatic group, an aromatic group, an alicyclic group, or a unit. Selected from the group consisting of substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups, P₁ A repeating unit containing P and₂The sum of repeating units containing₁Iterate with Unit and P₂A repeating unit containing P and_ThreeAbout 2 to about 90% of the sum of repeating units, P₂Including The number of repeating units is P₁A repeating unit containing P and₂About 5 to about 9 of the number of repeating units containing 5%, but P₁A repeating unit containing P and₂The number of repeating units containing₁Anti-including Return unit and P₂A repeating unit containing P and_ThreeAt least 1% of each of the number of repeating units ) Polyamines containing repeating units of. 46. P₁A repeating unit containing P and₂Is the sum of repeating units containing₁A repeating unit containing P and₂To Including repeating unit and P_Three47. The method of claim 45, which is about 10 to about 85% of the sum of repeating units. Polyamine. 47. The substituted aliphatic, substituted aromatic and substituted alicyclic group substituents, (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic group, Selected from the group consisting of aromatic groups and alicyclic groups, m is an integer from 0 to 4 , N is an integer from 1 to 7) and mixtures thereof. The polyamine according to claim 45. 48. The polyamine has the formula: 46. The polyamine of claim 45, which is essentially free of repeating units of. 49. The polyamine has the formula: 46. The polyamine of claim 45, which is essentially free of repeating units of. 50. formula: (In the formula, P₁A repeating unit containing P and P₂Repeating units containing Representing a repeating unit of a polymer containing natively aminated olefinic unsaturation, P_Three Is the reaction of the same polymer containing olefinic unsaturation with reactive carbon-carbon double bonds. Represents a subunit, and R, R ', R "and R'" are independently an aliphatic group, an aromatic group, or an alicyclic group. Selected from the group consisting of formula groups, substituted aliphatic groups, substituted aromatic groups and substituted alicyclic groups However, -NRR 'is different from -NR "R'", and₁A repeating unit containing P and₂Including The sum of repeating units is P₁A repeating unit containing P and₂A repeating unit containing P and_ThreeSum of repeating units 2 to about 90% of P,₁The number of repeating units containing₁A repeating unit containing P and₂Including It is about 5 to about 95% of the total number of repeating units, provided that P₁A repeating unit containing P and₂Including The number of repeating units is P₁A repeating unit containing P and₂Unit repeats including P and_ThreeNumber of repeating units Of at least 1% of each of the above). 51. P₁A repeating unit containing P and₂Is the sum of repeating units containing₁A repeating unit containing P and₂To Including repeating unit and P_Three51. The about 50 to about 85% of the sum of repeating units. Polyamine. 52. The substituted aliphatic, substituted aromatic and substituted alicyclic group substituents, (Where R₁, R₂, R_Three, R_FiveAnd R₆Are independently hydrogen, aliphatic groups, aromatic groups and Selected from the group consisting of alicyclic groups, provided that R₁And R₂At least one of R and_Five And R₆At least one of R is other than hydrogen, and R_FourIs an aliphatic or aromatic group And an alicyclic group, m is an integer of 0 to 4, and n is 1 Is an integer of ~ 7) and mixtures thereof. The polyamine according to. 53. The polyamine has the formula: 51. The polyamine of claim 50 which is essentially free of repeating units of.